WO2014024735A1 - Ink composition, ink-composition production method, transparent conductive film, and transparent-conductive-film production method - Google Patents

Ink composition, ink-composition production method, transparent conductive film, and transparent-conductive-film production method Download PDF

Info

Publication number
WO2014024735A1
WO2014024735A1 PCT/JP2013/070637 JP2013070637W WO2014024735A1 WO 2014024735 A1 WO2014024735 A1 WO 2014024735A1 JP 2013070637 W JP2013070637 W JP 2013070637W WO 2014024735 A1 WO2014024735 A1 WO 2014024735A1
Authority
WO
WIPO (PCT)
Prior art keywords
ink composition
weight
pedot
parts
aqueous solution
Prior art date
Application number
PCT/JP2013/070637
Other languages
French (fr)
Japanese (ja)
Inventor
順彦 佐々木
由宗 鈴木
Original Assignee
アルプス電気株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by アルプス電気株式会社 filed Critical アルプス電気株式会社
Publication of WO2014024735A1 publication Critical patent/WO2014024735A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/13—Morphological aspects
    • C08G2261/135—Cross-linked structures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/51—Charge transport
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/76—Post-treatment crosslinking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/79—Post-treatment doping
    • C08G2261/794—Post-treatment doping with polymeric dopants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/91—Photovoltaic applications
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/92—TFT applications
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/95—Use in organic luminescent diodes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond

Definitions

  • the present invention relates to an ink composition used for the production of a transparent conductive film, a method for producing the ink composition, a transparent conductive film, and a method for producing the transparent conductive film, and is suitably used for, for example, forming a transparent conductive film of a screen printing method.
  • the present invention relates to an ink composition, a method for producing an ink composition, a transparent conductive film, and a method for producing a transparent conductive film.
  • Transparent conductive films are used in the fields of liquid crystal displays, electroluminescence displays, plasma displays, electrochromic displays, solar cells, touch panels and the like.
  • a conductive inorganic material such as ITO (indium-tin oxide) or a conductive organic material such as polyethylenedioxythiophene (PEDOT) / polystyrene sulfonic acid (PSS) is used.
  • PEDOT polyethylenedioxythiophene
  • PSS polystyrene sulfonic acid
  • the transparent conductive film using the conductive organic material one using an ink composition containing a PEDOT / PSS aqueous solution has been proposed (for example, see Patent Document 1).
  • the ink composition described in Patent Document 1 by including a silane coupling agent, it is possible to form a coating film having excellent wear resistance and moisture resistance and high conductivity.
  • the ink composition described in Patent Document 1 is formed by a wet process. In this wet process, it is desirable to use a screen printing method capable of reducing the cost. In this screen printing method, a high viscosity of several hundred cp or more is required at a cone rotation speed of 5 rpm of the rotational viscometer. On the other hand, the ink composition described in Patent Document 1 has a problem that it is not suitable for the screen printing method because the viscosity of the ink composition is low (10 cp or less).
  • the conventional ink composition it is possible to adjust the viscosity to a high viscosity suitable for the screen printing method by adding various electrically insulating polymer binders as a thickener.
  • various electrically insulating polymer binders as a thickener.
  • the conductivity of the transparent conductive film obtained from the ink composition decreases (specific resistance). Increase).
  • it is necessary to increase the film thickness, the decrease in the transparent conductive film due to the increase in the film thickness, the decrease in display visibility, and the electrode pattern of the transparent conductive film There was a problem of being visually recognized.
  • the present invention has been made in view of the above points, and is capable of forming a transparent conductive film by a screen printing method.
  • the ink composition of the present invention is formed by converting a solution obtained by mixing 100 parts by weight of a PEDOT / PSS aqueous solution, 300 parts by weight or less of a mixed alcohol, and a silane coupling agent, and the concentration of the PEDOT / PSS aqueous solution is The relational expression (1) is satisfied, and the mixed alcohol includes a low viscosity solvent and a high viscosity alcohol.
  • Formula (1) 1.3 wt% ⁇ PEDOT / PSS aqueous solution ⁇ 3.5 wt%
  • the concentration range in which gelation can be realized shifts to the low concentration side.
  • the PEDOT / PSS aqueous solution is in an appropriate gelation state within a range satisfying the above formula (1), so that the ink composition is suitable for screen printing without adding various polymer binders as a thickener. A highly viscous solution.
  • the low viscosity solvent is preferably a lower alcohol.
  • the low viscosity solvent is preferably methanol, ethanol or propanol.
  • the low-viscosity solvent is preferably glycol monoalkyl ether.
  • the highly viscous alcohol is preferably glycol.
  • the glycol is preferably propylene glycol or butanediol.
  • the ink composition of the present invention preferably contains 100 parts by weight of the PEDOT / PSS aqueous solution and 300 parts by weight of the mixed alcohol.
  • the mixing ratio of the low viscosity solvent and the high viscosity alcohol is preferably 4: 1.
  • the concentration of the PEDOT / PSS aqueous solution satisfies the following relational expression (2), and the mixed alcohol is 100 to 150 parts by weight of the low-viscosity solvent and 200 parts by weight of the high-viscosity alcohol. It is preferable that it contains 150 parts by weight or more.
  • Formula (2) 1.3 wt% ⁇ PEDOT / PSS aqueous solution ⁇ 2.0 wt%
  • the concentration of the PEDOT / PSS aqueous solution satisfies the following relational expression (3), and the mixed alcohol is 15 to 180 parts by weight of the low-viscosity solvent and 285 parts by weight of the high-viscosity alcohol. It is preferable that it contains 120 parts by weight or less.
  • Formula (3) 2.0 wt% ⁇ PEDOT / PSS aqueous solution ⁇ 3.0 wt%
  • the concentration of the PEDOT / PSS aqueous solution satisfies the following relational expression (4), and the mixed alcohol is 10 to 200 parts by weight of the low-viscosity solvent and 290 parts by weight of the high-viscosity alcohol. It is preferable that it contains 100 parts by weight or less.
  • Formula (4) 3.0 wt% ⁇ PEDOT / PSS aqueous solution ⁇ 3.5 wt%
  • the concentration of the PEDOT / PSS aqueous solution satisfies the following relational expression (2), and the mixed alcohol is 80 to 200 parts by weight of the low-viscosity solvent and 20 parts by weight of the high-viscosity alcohol. It is preferable that it contains 50 parts by weight or less.
  • Formula (2) 1.3 wt% ⁇ PEDOT / PSS aqueous solution ⁇ 2.0 wt%
  • the concentration of the PEDOT / PSS aqueous solution satisfies the following relational expression (3), and the mixed alcohol is 10 parts by weight or more and 220 parts by weight or less of the low viscosity solvent and 2 parts by weight of the high viscosity alcohol. It is preferable that it contains 55 parts by weight or less.
  • Formula (3) 2.0 wt% ⁇ PEDOT / PSS aqueous solution ⁇ 3.0 wt%
  • the concentration of the PEDOT / PSS aqueous solution satisfies the following relational expression (4), and the mixed alcohol is 5 parts by weight or more and 250 parts by weight or less of the low viscosity solvent and 1 part by weight of the high viscosity alcohol. It is preferable that it contains 65 parts by weight or less.
  • Formula (4) 3.0 wt% ⁇ PEDOT / PSS aqueous solution ⁇ 3.5 wt%
  • the method for producing an ink composition of the present invention is a method for producing the ink composition, wherein the solution containing the PEDOT / PSS aqueous solution, the mixed alcohol, and the silane coupling agent is stirred to gel. And a gelation step of producing an ink composition by converting the gelled solution into an ink.
  • a solution containing the PEDOT / PSS aqueous solution, the mixed alcohol, and the silane coupling agent becomes an appropriate gelation state without adding a thickener such as a binder polymer.
  • the viscosity of the ink composition can be adjusted to an appropriate range, so that an ink composition suitable for a screen printing method can be produced.
  • this ink composition has increased viscosity without containing an insulating polymer binder, it becomes possible to produce a transparent conductive film having high conductivity.
  • the transparent conductive film of the present invention is formed using the above ink composition.
  • the method for producing a transparent conductive film of the present invention is characterized by using the ink composition produced by the method for producing an ink composition.
  • an ink composition capable of forming a transparent conductive film by a screen printing method and obtaining a transparent conductive film excellent in conductivity and transmittance, a method for producing the ink composition, a transparent conductive film, and The manufacturing method of a transparent conductive film is realizable.
  • Examples of the conductive organic material used for forming the transparent conductive film include an ink composition containing a PEDOT / PSS aqueous solution and a silane coupling agent.
  • This ink composition can be formed into a transparent conductive film by screen printing with excellent production cost by adding various insulating polymer binders to increase the viscosity.
  • various insulating polymer binders when various insulating polymer binders are added, it is necessary to increase the film thickness of the transparent conductive film, which reduces the light transmittance of the transparent conductive film and the visibility of the conductive pattern by the transparent conductive film. Decrease is a problem.
  • the present inventors are suitable even in a region where the PEDOT / PSS aqueous solution has a low concentration. It was found that gelation proceeds. Then, the present inventors converted this appropriately gelled solution into an ink to form an ink composition, thereby forming a transparent conductive film for screen printing without using a thickener such as various polymer binders. The present inventors have found that an ink composition that is suitable and excellent in electrical conductivity and light transmittance can be realized, and has completed the present invention.
  • the ink composition according to the present invention is an ink composition obtained by mixing 100 parts by weight of an aqueous PEDOT / PSS solution, 300 parts by weight or less of a mixed alcohol, and a silane coupling agent.
  • the following relational expression (1) is satisfied, and the mixed alcohol includes a low viscosity solvent and a high viscosity alcohol.
  • Formula (1) 1.3 wt% ⁇ PEDOT / PSS aqueous solution ⁇ 3.5 wt%
  • the ink composition of the present invention since a predetermined amount of mixed alcohol containing a low-viscosity solvent and a high-viscosity alcohol is contained, a predetermined amount of PEDOT / PSS aqueous solution, a predetermined amount of mixed alcohol, and a silane coupling agent are added.
  • the concentration range of the appropriate gelation of the contained solution is shifted to the lower concentration side.
  • the PEDOT / PSS aqueous solution is in an appropriate gelation state within a range satisfying the above formula (1), so that the ink composition is suitable for screen printing without adding various polymer binders as a thickener.
  • a highly viscous solution since a predetermined amount of mixed alcohol containing a low-viscosity solvent and a high-viscosity alcohol is contained, a predetermined amount of PEDOT / PSS aqueous solution, a predetermined amount of mixed alcohol, and a silane coupling agent are added.
  • the concentration range of the appropriate gelation of the contained solution is
  • “appropriate gelation state” means a state in which a solution containing a predetermined amount of PEDOT / PSS aqueous solution, a predetermined amount of mixed alcohol and a silane coupling agent is gelled, and high viscosity. Any solution state shall be included.
  • the gelled state may be a state where a part of the solution is gelled, or may be a state where all of the solution is gelled and solidified.
  • FIG. 1 is a conceptual diagram of an ink composition according to the present invention.
  • a cross-link is formed by the silane coupling agent 13 as a binder between the PEDOT 11 as a conductive polymer compound and the PSS 12 as a polymer charge transfer complex.
  • The By this cross-linking, a three-dimensional network through a silane coupling agent is formed between the conductive compounds including PEDOT11 and PSS12, so that the film strength of the transparent conductive film formed using the ink composition Will improve.
  • the PEDOT / PSS aqueous solution satisfies the above formula (1) and contains a predetermined amount of mixed alcohol
  • the PEDOT / PSS is appropriately dispersed and the above 3
  • the mixed alcohol molecules enter between the dimensional networks to form an appropriate gel state. Since the viscosity of the ink composition can be appropriately improved by this appropriate gelation state, the viscosity of the ink composition can be increased to an extent necessary for forming a transparent conductive film by a screen printing method.
  • the necessary conductivity of the transparent conductive film can be ensured without increasing the film thickness of the transparent conductive film, thereby reducing the transmittance of the transparent conductive film and the visibility of the conductive pattern formed by the transparent conductive film. Is possible.
  • FIG. 2 is an explanatory diagram of the interaction between molecules of PEDOT / PSS in the ink composition according to the present invention
  • FIG. 3 is a diagram showing an infrared absorption spectrum of the transparent conductive film according to the present invention.
  • an interaction via sulfur atoms occurs between the PEDOT molecule 21 and the PSS molecule 22 (see the dotted line in FIG. 2).
  • the state where the PEDOT 11 is arranged along the PSS 12 shown in FIG. 1 corresponds to this.
  • an appropriate gelation state that can be obtained in a high-viscosity solution is the proximity due to Coulomb interaction mainly in the presence of a low-viscosity solvent or high-viscosity alcohol to which PSS molecules 22 of an ionic polymer are added at a predetermined ratio. This is a state where distance order is formed.
  • PEDOT / PSS aqueous solution various PEDOT / PSS aqueous solutions can be used as long as the concentration range shown in the above formula (1) is satisfied.
  • this PEDOT / PSS you may use a commercial item as it is.
  • Examples of commercially available PEDOT / PSS aqueous solutions include Clevios (registered trademark: manufactured by Heraeus) P, Clevios PH500, and Clevios PH1000.
  • silane coupling agent various silane coupling agents can be used as long as they can be used as a binder within the scope of the effects of the present invention.
  • silane coupling agent for example, dialkoxysilane containing an epoxy group, trialkoxysilane containing an epoxy group, and the like can be used.
  • diepoxysilane containing an epoxy group for example, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and the like can be used.
  • triepoxysilane containing an epoxy group examples include 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl). Examples thereof include ethyltriethoxysilane.
  • the mixed alcohol a mixture of a low viscosity solvent and a high viscosity alcohol is used.
  • the low viscosity solvent has a viscosity of less than 2.5 cp
  • the high viscosity alcohol has a viscosity of 20 cp or more.
  • the low viscosity solvent is not particularly limited as long as the effects of the present invention are achieved.
  • the mixed alcohol is 300 parts by weight or less with respect to 100 parts by weight of the PEDOT / PSS aqueous solution. Thereby, the ink composition can be appropriately gelled. Moreover, it is preferable that mixed alcohol exists in the range of 100 to 300 weight part with respect to 100 weight part of PEDOT / PSS aqueous solution.
  • a lower alcohol for example, methanol, ethanol or propanol is preferable. By using this lower alcohol, an appropriate gelled state can be easily obtained.
  • propanol 1-propanol or 2-propanol (isopropanol) may be used.
  • glycol monoalkyl ether is one in which one hydroxyl group of glycol is etherified, and since one hydroxyl group remains, it has characteristics close to that of alcohol, so the same effect as lower alcohol can be obtained.
  • examples of the glycol monoalkyl ether include propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, and ethylene glycol monomethyl ether.
  • the high-viscosity alcohol is not particularly limited as long as it has the effects of the present invention.
  • various diol compounds can be used as the highly viscous alcohol.
  • the high viscosity alcohol it is preferable to use ethylene glycol, propylene glycol, butanediol, or diethylene glycol, and more preferable is propylene glycol or butanediol.
  • a highly viscous solvent as an enhancer may be used as long as the effects of the present invention are achieved.
  • highly viscous compounds include dimethyl sulfoxide (DMSO).
  • the present inventors examined in detail the relationship between the composition of the ink composition and gelation.
  • Table 1 a commercially available PEDOT / PSS aqueous solution (trade name: Clevios (registered trademark) P (concentration 1.8% by weight)) was used, and PEDOT / PSD was diluted by water or concentrated by heating.
  • the relationship between the PEDOT / PSS concentration and the composition of the mixed alcohol (alcohol and glycol) and the appropriate gelation state when the PSS concentration is changed will be described.
  • the silane coupling agent is used in an amount equivalent to the solid content of PEDOT / PSS.
  • the amount of the mixed alcohol is changed by setting the mixing ratio (IPA: PG) of isopropanol (IPA) as the low viscosity solvent and propylene glycol (PG) as the high viscosity alcohol to 4: 1.
  • the composition ratio of the low-viscosity solvent and the high-viscosity alcohol is changed by setting the total amount of the mixed alcohol to 300 parts by weight with respect to 100 parts by weight of the PEDOT / PSS aqueous solution.
  • the concentration of the PEDOT / PSS aqueous solution to be used is in the range of 1.3% by weight or more, so that the ink composition is mixed and appropriately gelled. It becomes possible to be in a state. Further, by setting the concentration of the aqueous PEDOT / PSS solution to be 3.5 or less, it is possible to prevent solidification of the entire solution, and it is possible to concentrate and collect the ink composition.
  • IPA low viscosity solvent
  • PG high viscosity alcohol
  • the mixed alcohol contains 100 to 150 parts by weight of the low-viscosity solvent and 200 to 150 parts by weight of the high-viscosity alcohol. It can be gelled.
  • Formula (2) 1.3 wt% ⁇ PEDOT / PSS aqueous solution ⁇ 2.0 wt%
  • mixed alcohol contains 15 to 180 weight part of low-viscosity solvent and 285 to 120 weight part of high-viscosity alcohol. It can be gelled in a range.
  • Formula (3) 2.0 wt% ⁇ PEDOT / PSS aqueous solution ⁇ 3.0 wt%
  • the mixed alcohol includes 10 to 200 parts by weight of the low-viscosity solvent and 290 to 100 parts by weight of the high-viscosity alcohol. It can be gelled in a range.
  • Formula (4) 3.0 wt% ⁇ PEDOT / PSS aqueous solution ⁇ 3.5 wt%
  • the mixed alcohol contains 80 to 200 parts by weight of the low-viscosity solvent and 20 to 50 parts by weight of the high-viscosity alcohol. It becomes possible to make it an appropriate gelation state.
  • Formula (2) 1.3 wt% ⁇ PEDOT / PSS aqueous solution ⁇ 2.0 wt%
  • mixed alcohol contains 10 to 220 weight part of low-viscosity solvent and 2 to 55 weight part or less of high-viscosity glycol. It becomes possible to make it a gelation state appropriately in the range.
  • Formula (3) 2.0 wt% ⁇ PEDOT / PSS aqueous solution ⁇ 3.0 wt%
  • the mixed alcohol includes 5 to 250 parts by weight of the low-viscosity solvent and 1 to 65 parts by weight of the high-viscosity alcohol. It becomes possible to make it an appropriate gelation state in the range.
  • Formula (4) 3.0 wt% ⁇ PEDOT / PSS aqueous solution ⁇ 3.5 wt%
  • the ink composition according to the present invention, by setting the PEDOT / PSS aqueous solution in a range that satisfies the above relational expression (1), the ink composition can be appropriately gel in a wide range with respect to the composition and total amount of the mixed alcohol. It becomes possible to make it into a conversion state. As a result, the viscosity of the ink composition can be made suitable for screen printing without using various non-conductive binder polymers, so that it is possible to obtain a transparent conductive film excellent in conductivity and transmittance. It becomes.
  • FIG. 4 is a flowchart showing an outline of the manufacturing process of the transparent conductive film according to the present embodiment.
  • the method for producing an ink according to the present invention includes a gelling step in which a PEDOT / PSS aqueous solution, a mixed alcohol, and a silane coupling agent are mixed to form a gel, and an ink composition is manufactured by converting the gel into an ink. An inking process.
  • DMSO dimethyl sulfoxide
  • aqueous solution containing only PEDOT / PSS aqueous solution containing only PEDOT / PSS
  • silane coupling agent equivalent to the solid content of PEDOT: PSS a silane coupling agent equivalent to the solid content of PEDOT: PSS
  • a predetermined composition PEDOT / PSS aqueous solution is prepared by adding mixed alcohol having (ST1, ST2). And after stirring and mixing this PEDOT / PSS aqueous solution for a predetermined time, stirring is stopped and it is left to stand for several hours to overnight, and let a mixed solution be a suitable gelled state (ST3, ST4). Next, in the ink forming step, the gelled solution is stirred for about 1 hour to make ink, thereby producing an ink composition (ST5).
  • the viscosity of the ink composition can be adjusted to an appropriate range by gelation without adding a thickener such as a binder polymer, which is suitable for screen printing.
  • An ink composition having a high viscosity (100 cp or more: stirring speed 5 rpm) can be produced. And since this ink composition has increased viscosity without containing an insulating polymer binder, it becomes possible to produce a transparent conductive film having high conductivity.
  • the ink composition according to the above embodiment contains a predetermined amount of mixed alcohol containing a low-viscosity solvent and a high-viscosity alcohol, so that a predetermined amount of PEDOT / PSS aqueous solution, a predetermined amount of Since the concentration range of the appropriate gelation state of the solution containing the mixed alcohol and the silane coupling agent shifts to the low concentration side, the gel state is in an appropriate range as long as the concentration of the aqueous solution of PEDOT / PSS satisfies the above formula (1). . By setting it to this appropriate gel state, the viscosity of the ink composition falls within a range suitable for screen printing, so there is no need to add various polymer binders as thickeners.
  • the viscosity of the ink composition can be increased without using a high-concentration binder or a high-viscosity solvent, the resistance and durability of the transparent conductive film obtained using the ink composition can be improved. Moreover, it becomes possible to perform baking at a low temperature (for example, 110 ° C. or less, 20 minutes).
  • the ink composition according to the present embodiment and the ink composition according to the comparative example were produced, and the characteristics of the produced ink compositions were evaluated. Moreover, the transparent conductive film was produced using the produced ink composition, and the physical property was evaluated. Below, various physical property measurement conditions are shown.
  • the viscosity was measured using a cone rotation type viscosity measuring device (trade name rheometer / viscosimeter, manufactured by HAAKE) RotoVisco 1 under the condition of a cone rotation speed of 5 rpm.
  • the sheet resistance of the transparent conductive film was the sheet resistance (sheet resistance value) obtained by measuring the surface resistance of the transparent conductive film using a four-probe type area resistance meter (LORESTA EP MCP-1360, manufactured by Mitsubishi Chemical Corporation).
  • the conductivity was determined by the product of the sheet resistance value and the film thickness.
  • the film thickness was measured on the step portion of the screen printing pattern using a contact type step meter (DEKTAK).
  • Total light transmittance and (Haze) The total light transmittance and haze of the transparent conductive film were measured using a haze meter (trade name HZ-2, manufactured by Suga Test Instruments Co., Ltd.). The total light transmittance was measured based on JIS-K7361-1, and haze was measured based on JIS-K7136.
  • the present inventors prepared an ink composition by changing the composition ratio of PEDOT and a mixed alcohol solution under the condition that the silane coupling agent was a constant amount, and the ink composition was obtained using the prepared ink composition.
  • the physical properties of the transparent conductive film were examined (Example 1 to Example 3, Comparative Example 1 and Comparative Example 2).
  • Example 1 (Preparation of ink composition)
  • the PEDOT / PSS aqueous solution a commercial product (Clevios P, manufactured by Heraeus) having a solid content of 1.8% by weight was used.
  • An aqueous solution was prepared by adding an equivalent amount of a silane coupling agent to the PEDOT / PSS solid content to this PEDOT / PSS aqueous solution.
  • 100 parts by weight of this aqueous solution 100 parts by weight of mixed alcohol (isopropanol (80 parts by weight): propylene glycol (20 parts by weight)) and 10 parts by weight of dimethyl sulfoxide (DMSO) as an enhancer were added.
  • the ink composition was prepared by stirring for 1 hour.
  • the obtained transparent conductive film had a film thickness of 860 nm, a sheet resistance of 370 ⁇ / ⁇ , a conductivity of 31 S / cm, a total light transmittance of 83.2%, and a haze of 1.0. It was. The results are shown in Table 3 below.
  • Example 2 (Adjustment of ink composition)
  • the ink composition was prepared in the same manner as in Example 1 except that the addition amount of dimethyl sulfoxide was 15 parts by weight and the mixed alcohol was 200 parts by weight (isopropanol (160 parts by weight): propylene glycol (40 parts by weight)). Produced.
  • This ink composition was brought into an appropriate gelation state as in Example 1.
  • the viscosity was 840 cp. The results are shown in Table 2 below.
  • a transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1.
  • the obtained transparent conductive film had a film thickness of 980 nm, an area resistance of 261 ⁇ / ⁇ , an electrical conductivity of 39 S / cm, a total light transmittance of 84.1%, and a haze of 1.0. It was. The results are shown in Table 3 below.
  • Example 3 (Adjustment of ink composition) Ink composition was the same as in Example 1 except that the addition amount of dimethyl sulfoxide was 17.5 parts by weight and the mixed alcohol was 250 parts by weight (isopropanol (200 parts by weight): propylene glycol (50 parts by weight)). A product was made. This ink composition was gelled as in Example 1. The viscosity was 580 cp. The results are shown in Table 2 below.
  • a transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1.
  • the obtained transparent conductive film had a film thickness of 890 nm, an area resistance of 261 ⁇ / ⁇ , an electrical conductivity of 26 S / cm, a total light transmittance of 80.2%, and a haze of 1.2. It was. The results are shown in Table 3 below.
  • a transparent conductive film was produced by screen printing in the same manner as in Example 1. Since the ink composition of Comparative Example 1 had a low viscosity, the flow of the ink composition was large during screen printing, and it was impossible to control the shape of the transparent conductive film.
  • the obtained transparent conductive film had a thickness of 300 nm, an area resistance of 1100 ⁇ / ⁇ , an electrical conductivity of 30 S / cm, a total light transmittance of 86.5%, and a haze of 0.9. It was. The results are shown in Table 3 below.
  • the inventors prepared an ink composition by changing the concentration of the aqueous PEDOT / PSS solution, the content of the silane coupling agent, and the content of the mixed alcohol, and obtained the ink composition using the ink composition thus prepared.
  • the physical properties of the obtained transparent conductive film were examined (Examples 4 to 11, Comparative Examples 3 to 5).
  • the transparent conductive film was produced using the commercially available ink composition, and the physical property of the produced transparent conductive film was investigated.
  • Example 4 (Adjustment of ink composition)
  • concentration of the aqueous PEDOT / PSS solution is 1.7% by weight
  • the silane coupling agent is 0.43 parts by weight
  • the amount of dimethyl sulfoxide added is 20 parts by weight
  • the mixed alcohol is 300 parts by weight (isopropanol (100 parts by weight)).
  • Propylene glycol (200 parts by weight)) an ink composition was prepared in the same manner as in Example 1. This ink composition was in an appropriate gelled state as in Example 1. The viscosity was 400 cp. The results are shown in Table 4 below.
  • a transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1.
  • the obtained transparent conductive film had a film thickness of 45 nm, a sheet resistance of 750 ⁇ / ⁇ , a conductivity of 290 S / cm, a total light transmittance of 87%, and a haze of 0.9. It was. The results are shown in Table 5 below.
  • Example 5 (Adjustment of ink composition) An ink composition was prepared in the same manner as in Example 4 except that the concentration of the PEDOT / PSS aqueous solution was 2.2 wt% and the silane coupling agent was 0.55 parts by weight. This ink composition was in an appropriate gelled state as in Example 4. The viscosity was 530 cp. The results are shown in Table 4 below.
  • a transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1.
  • the obtained transparent conductive film had a film thickness of 60 nm, a sheet resistance of 343 ⁇ / ⁇ , a conductivity of 490 S / cm, a total light transmittance of 88%, and a haze of 0.8. It was. The results are shown in Table 5 below.
  • Example 6> Adjustment of ink composition
  • concentration of the aqueous solution of PEDOT / PSS was 2.5% by weight
  • the silane coupling agent was 0.63 parts by weight
  • the mixed alcohol was 300 parts by weight (isopropanol (60 parts by weight): propylene glycol (240 parts by weight)).
  • an ink composition was prepared in the same manner as in Example 4.
  • This ink composition was in an appropriate gelled state as in Example 4.
  • the viscosity was 600 cp.
  • Table 4 The results are shown in Table 4 below.
  • a transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1.
  • the obtained transparent conductive film had a film thickness of 75 nm, a sheet resistance of 290 ⁇ / ⁇ , a conductivity of 460 S / cm, a total light transmittance of 88%, and a haze of 0.8. It was. The results are shown in Table 5 below.
  • Example 7 (Adjustment of ink composition) The concentration of the PEDOT / PSS aqueous solution was 2.5% by weight, the silane coupling agent was 0.63 parts by weight, and the mixed alcohol was 300 parts by weight (isopropanol (50 parts by weight): propylene glycol (250 parts by weight)). Except for this, an ink composition was prepared in the same manner as in Example 4. This ink composition was in an appropriate gelled state as in Example 1. The viscosity was 600 cp. The results are shown in Table 4 below.
  • a transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1.
  • the obtained transparent conductive film had a film thickness of 72 nm, a sheet resistance of 260 ⁇ / ⁇ , a conductivity of 533 S / cm, a total light transmittance of 88%, and a haze of 0.8. It was. The results are shown in Table 5 below.
  • Example 8> Adjustment of ink composition
  • the concentration of the aqueous solution of PEDOT / PSS was 2.6% by weight
  • the silane coupling agent was 0.65 parts by weight
  • the mixed alcohol was 300 parts by weight (isopropanol (130 parts by weight): propylene glycol (170 parts by weight)).
  • an ink composition was prepared in the same manner as in Example 4.
  • This ink composition was in an appropriate gelled state as in Example 1.
  • the viscosity was 660 cp.
  • Table 4 The results are shown in Table 4 below.
  • a transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1.
  • the obtained transparent conductive film had a film thickness of 80 nm, a sheet resistance of 250 ⁇ / ⁇ , a conductivity of 500 S / cm, a total light transmittance of 87%, and a haze of 0.9. It was. The results are shown in Table 5 below.
  • Example 9 (Adjustment of ink composition) The concentration of the aqueous PEDOT / PSS solution was 2.8% by weight, the silane coupling agent was 0.70 part by weight, and the mixed alcohol was 300 parts by weight (isopropanol (40 parts by weight): propylene glycol (260 parts by weight)). Except for this, an ink composition was prepared in the same manner as in Example 4. This ink composition was in an appropriate gelled state as in Example 1. The viscosity was 790 cp. The results are shown in Table 4 below.
  • a transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1.
  • the obtained transparent conductive film had a film thickness of 105 nm, a sheet resistance of 210 ⁇ / ⁇ , a conductivity of 453 S / cm, a total light transmittance of 86%, and a haze of 0.9. It was. The results are shown in Table 5 below.
  • Example 10> Adjustment of ink composition
  • concentration of the PEDOT / PSS aqueous solution was 2.9% by weight
  • silane coupling agent was 0.73 parts by weight
  • the mixed alcohol was 300 parts by weight (isopropanol (140 parts by weight): propylene glycol (160 parts by weight)).
  • an ink composition was prepared in the same manner as in Example 4. This ink composition was in an appropriate gelled state as in Example 1. The viscosity was 830 cp. The results are shown in Table 4 below.
  • a transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1.
  • the obtained transparent conductive film had a thickness of 120 nm, an area resistance of 205 ⁇ / ⁇ , an electrical conductivity of 407 S / cm, a total light transmittance of 85%, and a haze of 1.0. It was. The results are shown in Table 5 below.
  • Example 11> Adjustment of ink composition
  • the concentration of the aqueous solution of PEDOT / PSS was 3.3% by weight
  • the silane coupling agent was 0.83 parts by weight
  • the mixed alcohol was 300 parts by weight (isopropanol (100 parts by weight): propylene glycol (200 parts by weight)).
  • an ink composition was prepared in the same manner as in Example 4.
  • This ink composition was in an appropriate gelled state as in Example 1.
  • the viscosity was 920 cp. The results are shown in Table 4 below.
  • a transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1.
  • the obtained transparent conductive film had a film thickness of 135 nm, a sheet resistance of 350 ⁇ / ⁇ , a conductivity of 211 S / cm, a total light transmittance of 84%, and a haze of 1.2. It was. The results are shown in Table 5 below.
  • Example 12 (Adjustment of ink composition) An ink composition was prepared in the same manner as in Example 7, except that the mixed alcohol was 300 parts by weight (propylene glycol monomethyl ether (50 parts by weight): propylene glycol (250 parts by weight)). This ink composition was in an appropriate gelled state as in Example 1. The viscosity was 560 cp. The results are shown in Table 4 below.
  • a transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1.
  • the obtained transparent conductive film had a film thickness of 64 nm, a sheet resistance of 300 ⁇ / ⁇ , a conductivity of 520 S / cm, a total light transmittance of 88%, and a haze of 0.8. It was. The results are shown in Table 5 below.
  • a transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1.
  • the obtained transparent conductive film had a film thickness of 27 nm, a sheet resistance of 1200 ⁇ / ⁇ , a conductivity of 309 S / cm, a total light transmittance of 88%, and a haze of 0.9. It was. The results are shown in Table 7 below.
  • a transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1.
  • the obtained transparent conductive film had a film thickness of 30 nm, a sheet resistance of 1200 ⁇ / ⁇ , a conductivity of 278 S / cm, a total light transmittance of 88%, and a haze of 0.9. It was. The results are shown in Table 7 below.
  • the present invention has an effect that a transparent conductive film can be formed by a screen printing method, and an ink composition capable of obtaining a transparent conductive film having excellent conductivity and transmittance and a method for producing the ink composition can be realized.
  • the present invention is applicable to devices using various transparent conductive films such as a liquid crystal display, an electroluminescence display, a plasma display, an electrochromic display, a transparent electrode and an electromagnetic wave shield used for solar cells, touch panels, and electronic paper.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Conductive Materials (AREA)
  • Non-Insulated Conductors (AREA)
  • Manufacturing Of Electric Cables (AREA)

Abstract

[Problem] To provide: an ink composition with which screen printing can be used to form a transparent conductive film exhibiting excellent conductivity and transmittance; an ink-composition production method; a transparent conductive film; and a transparent-conductive-film production method. [Solution] This ink composition is characterized by being obtained by forming an ink from a solution obtained by mixing 100 parts by weight of a PEDOT/PSS aqueous solution, 300 or fewer parts by weight of a mixed alcohol, and a silane coupling agent. This ink composition is further characterized in that: the concentration of the PEDOT/PSS aqueous solution satisfies relational expression (1), namely 1.3 wt% ≤ PEDOT/PSS aqueous solution < 3.5 wt%; and the mixed alcohol includes a low-viscosity solvent and a high-viscosity alcohol. It is preferable that the low-viscosity solvent in this ink composition be a lower alcohol. Furthermore, it is preferable that the high-viscosity alcohol in this ink composition be glycol.

Description

インク組成物、インク組成物の製造方法、透明導電膜及び透明導電膜の製造方法Ink composition, method for producing ink composition, transparent conductive film, and method for producing transparent conductive film
　本発明は、透明導電膜の製造に用いられるインク組成物、インク組成物の製造方法、透明導電膜及び透明導電膜の製造方法に関し、例えば、スクリーン印刷方式の透明導電膜の形成に好適に用いられるインク組成物、インク組成物の製造方法、透明導電膜及び透明導電膜の製造方法に関する。 The present invention relates to an ink composition used for the production of a transparent conductive film, a method for producing the ink composition, a transparent conductive film, and a method for producing the transparent conductive film, and is suitably used for, for example, forming a transparent conductive film of a screen printing method. The present invention relates to an ink composition, a method for producing an ink composition, a transparent conductive film, and a method for producing a transparent conductive film.
　液晶ディスプレイ、エレクトロルミネッセンスディスプレイ、プラズマディスプレイ、エレクトロクロミックディスプレイ、太陽電池、タッチパネルなどの分野では、透明導電膜が用いられている。透明導電膜の材料としては、ＩＴＯ（インジウム－スズ酸化物）などの導電性無機材料や、ポリエチレンジオキシチオフェン（ＰＥＤＯＴ）／ポリスチレンスルホン酸（ＰＳＳ）などの導電性有機材料が用いられている。この導電性有機材料を用いた透明導電膜としては、ＰＥＤＯＴ／ＰＳＳ水溶液を含むインク組成物を用いたものが提案されている（例えば、特許文献１参照）。特許文献１に記載のインク組成物においては、シランカップリング剤を含むことにより、耐摩耗性や耐湿性に優れ、且つ高導電性である塗布膜を形成することが可能となる。 Transparent conductive films are used in the fields of liquid crystal displays, electroluminescence displays, plasma displays, electrochromic displays, solar cells, touch panels and the like. As a material for the transparent conductive film, a conductive inorganic material such as ITO (indium-tin oxide) or a conductive organic material such as polyethylenedioxythiophene (PEDOT) / polystyrene sulfonic acid (PSS) is used. As the transparent conductive film using the conductive organic material, one using an ink composition containing a PEDOT / PSS aqueous solution has been proposed (for example, see Patent Document 1). In the ink composition described in Patent Document 1, by including a silane coupling agent, it is possible to form a coating film having excellent wear resistance and moisture resistance and high conductivity.
特開２００５－１４５９８７号公報JP 2005-145987 A
　ところで、特許文献１に記載のインク組成物は、ウェットプロセスで成膜される。このウェットプロセスにおいては、低コスト化が可能なスクリーン印刷方式を用いることが望ましい。このスクリーン印刷方式では、回転粘度計のコーン回転速度５ｒｐｍにおいて、数１００ｃｐ以上の高粘度が要求される。一方で、特許文献１に記載のインク組成物は、インク組成物の粘度が低い（１０ｃｐ以下）ことから、スクリーン印刷方式には適さない問題がある。 Incidentally, the ink composition described in Patent Document 1 is formed by a wet process. In this wet process, it is desirable to use a screen printing method capable of reducing the cost. In this screen printing method, a high viscosity of several hundred cp or more is required at a cone rotation speed of 5 rpm of the rotational viscometer. On the other hand, the ink composition described in Patent Document 1 has a problem that it is not suitable for the screen printing method because the viscosity of the ink composition is low (10 cp or less).
　また、従来のインク組成物においては、電気的に絶縁性の各種ポリマーバインダーを増粘剤として添加することにより、スクリーン印刷方式に適した高粘度に調整することは可能となる。しかしながら、従来のインク組成物においてスクリーン印刷方式に用いる場合には、インク組成物に各種ポリマーバインダーを多量に添加する必要があり、インク組成物から得られる透明導電膜の導電率が低下（比抵抗が増加）する。このため、面積抵抗を目標値に適合させるためには、膜厚を厚くすることが必要となり、膜厚の増大による透明導電膜の低下や、表示の視認性の低下及び透明導電膜の電極パターンが視認される問題があった。 In addition, in the conventional ink composition, it is possible to adjust the viscosity to a high viscosity suitable for the screen printing method by adding various electrically insulating polymer binders as a thickener. However, when used in a screen printing method in a conventional ink composition, it is necessary to add a large amount of various polymer binders to the ink composition, and the conductivity of the transparent conductive film obtained from the ink composition decreases (specific resistance). Increase). For this reason, in order to adapt the sheet resistance to the target value, it is necessary to increase the film thickness, the decrease in the transparent conductive film due to the increase in the film thickness, the decrease in display visibility, and the electrode pattern of the transparent conductive film There was a problem of being visually recognized.
　本発明は、かかる点に鑑みてなされたものであり、スクリーン印刷方式による透明導電膜の形成が可能であり、しかも導電率及び透過率に優れた透明導電膜が得られるインク組成物、インク組成物の製造方法、透明導電膜及び透明導電膜の製造方法を提供することを目的とする。 The present invention has been made in view of the above points, and is capable of forming a transparent conductive film by a screen printing method. In addition, an ink composition and an ink composition from which a transparent conductive film excellent in conductivity and transmittance can be obtained. It aims at providing the manufacturing method of a thing, the transparent conductive film, and the manufacturing method of a transparent conductive film.
　本発明のインク組成物は、ＰＥＤＯＴ／ＰＳＳ水溶液１００重量部と、混合アルコール３００重量部以下と、シランカップリング剤と、を混合した溶液をインク化してなり、前記ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が下記関係式（１）を満たし、前記混合アルコールが低粘性溶媒と高粘性アルコールとを含むことを特徴とする。
式（１）
　１．３重量％≦ＰＥＤＯＴ／ＰＳＳ水溶液＜３．５重量％ The ink composition of the present invention is formed by converting a solution obtained by mixing 100 parts by weight of a PEDOT / PSS aqueous solution, 300 parts by weight or less of a mixed alcohol, and a silane coupling agent, and the concentration of the PEDOT / PSS aqueous solution is The relational expression (1) is satisfied, and the mixed alcohol includes a low viscosity solvent and a high viscosity alcohol.
Formula (1)
1.3 wt% ≦ PEDOT / PSS aqueous solution <3.5 wt%
　この構成によれば、低粘性溶媒と高粘性アルコールとを含む混合アルコールを所定量含有することから、所定量のＰＥＤＯＴ／ＰＳＳ水溶液、所定量の混合アルコール及びシランカップリング剤を含む溶液の適切なゲル化を実現できる濃度範囲が低濃度側にシフトする。これにより、ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が上記式（１）を満たす範囲で適切なゲル化状態となるので、増粘剤としての各種ポリマーバインダーを添加することなく、インク組成物がスクリーン印刷に適した高粘度溶液となる。そして、非導電性の各種ポリマーバインダーを添加することなくスクリーン印刷が可能となるので、インク組成物から得られた透明導電膜の膜厚の増大を防ぐことが可能となると共に、絶縁抵抗の増大を防ぐことができる。この結果、絶縁抵抗値に優れた透明導電膜を実現することができる。 According to this configuration, since a predetermined amount of the mixed alcohol containing the low-viscosity solvent and the high-viscosity alcohol is contained, an appropriate amount of the solution containing the predetermined amount of the PEDOT / PSS aqueous solution, the predetermined amount of the mixed alcohol, and the silane coupling agent is appropriate. The concentration range in which gelation can be realized shifts to the low concentration side. As a result, the PEDOT / PSS aqueous solution is in an appropriate gelation state within a range satisfying the above formula (1), so that the ink composition is suitable for screen printing without adding various polymer binders as a thickener. A highly viscous solution. Since screen printing can be performed without adding various non-conductive polymer binders, it is possible to prevent an increase in the thickness of the transparent conductive film obtained from the ink composition and increase the insulation resistance. Can be prevented. As a result, a transparent conductive film having an excellent insulation resistance value can be realized.
　本発明のインク組成物においては、低粘性溶媒が低級アルコールであることが好ましい。 In the ink composition of the present invention, the low viscosity solvent is preferably a lower alcohol.
　本発明のインク組成物においては、前記低粘性溶媒がメタノール、エタノール又はプロパノールであることが好ましい。 In the ink composition of the present invention, the low viscosity solvent is preferably methanol, ethanol or propanol.
　本発明のインク組成物においては、前記低粘性溶媒がグリコールモノアルキルエーテルであるこが好ましい。 In the ink composition of the present invention, the low-viscosity solvent is preferably glycol monoalkyl ether.
　本発明のインク組成物においては、前記高粘性アルコールがグリコールであることが好ましい。 In the ink composition of the present invention, the highly viscous alcohol is preferably glycol.
　本発明のインク組成物においては、前記グリコールがプロピレングリコール又はブタンジオールであることが好ましい。 In the ink composition of the present invention, the glycol is preferably propylene glycol or butanediol.
　本発明のインク組成物においては、前記ＰＥＤＯＴ／ＰＳＳ水溶液１００重量部と、前記混合アルコール３００重量部と、を含むことが好ましい。 The ink composition of the present invention preferably contains 100 parts by weight of the PEDOT / PSS aqueous solution and 300 parts by weight of the mixed alcohol.
　本発明のインク組成物においては、前記低粘性溶媒と前記高粘性アルコールとの混合比（低粘性溶媒：高粘性アルコール）が４：１であることが好ましい。 In the ink composition of the present invention, the mixing ratio of the low viscosity solvent and the high viscosity alcohol (low viscosity solvent: high viscosity alcohol) is preferably 4: 1.
　本発明のインク組成物においては、前記ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が下記関係式（２）を満たし、前記混合アルコールが前記低粘性溶媒１００重量部以上１５０重量部以下と前記高粘性アルコール２００重量部以上１５０重量部以下とを含むことが好ましい。
式（２）
　１．３重量％≦ＰＥＤＯＴ／ＰＳＳ水溶液＜２．０重量％ In the ink composition of the present invention, the concentration of the PEDOT / PSS aqueous solution satisfies the following relational expression (2), and the mixed alcohol is 100 to 150 parts by weight of the low-viscosity solvent and 200 parts by weight of the high-viscosity alcohol. It is preferable that it contains 150 parts by weight or more.
Formula (2)
1.3 wt% ≦ PEDOT / PSS aqueous solution <2.0 wt%
　本発明のインク組成物においては、前記ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が下記関係式（３）を満たし、前記混合アルコールが前記低粘性溶媒１５重量部以上１８０重量部以下と前記高粘性アルコール２８５重量部以上１２０重量部以下とを含むことが好ましい。
式（３）
　２．０重量％≦ＰＥＤＯＴ／ＰＳＳ水溶液＜３．０重量％ In the ink composition of the present invention, the concentration of the PEDOT / PSS aqueous solution satisfies the following relational expression (3), and the mixed alcohol is 15 to 180 parts by weight of the low-viscosity solvent and 285 parts by weight of the high-viscosity alcohol. It is preferable that it contains 120 parts by weight or less.
Formula (3)
2.0 wt% ≦ PEDOT / PSS aqueous solution <3.0 wt%
　本発明のインク組成物においては、前記ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が下記関係式（４）を満たし、前記混合アルコールが前記低粘性溶媒１０重量部以上２００重量部以下と前記高粘性アルコール２９０重量部以上１００重量部以下とを含むことが好ましい。
式（４）
　３．０重量％≦ＰＥＤＯＴ／ＰＳＳ水溶液＜３．５重量％ In the ink composition of the present invention, the concentration of the PEDOT / PSS aqueous solution satisfies the following relational expression (4), and the mixed alcohol is 10 to 200 parts by weight of the low-viscosity solvent and 290 parts by weight of the high-viscosity alcohol. It is preferable that it contains 100 parts by weight or less.
Formula (4)
3.0 wt% ≦ PEDOT / PSS aqueous solution <3.5 wt%
　本発明のインク組成物においては、前記ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が下記関係式（２）を満たし、前記混合アルコールが前記低粘性溶媒８０重量部以上２００重量部以下と前記高粘性アルコール２０重量部以上５０重量部以下とを含むことが好ましい。
式（２）
　１．３重量％≦ＰＥＤＯＴ／ＰＳＳ水溶液＜２．０重量％ In the ink composition of the present invention, the concentration of the PEDOT / PSS aqueous solution satisfies the following relational expression (2), and the mixed alcohol is 80 to 200 parts by weight of the low-viscosity solvent and 20 parts by weight of the high-viscosity alcohol. It is preferable that it contains 50 parts by weight or less.
Formula (2)
1.3 wt% ≦ PEDOT / PSS aqueous solution <2.0 wt%
　本発明のインク組成物においては、前記ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が下記関係式（３）を満たし、前記混合アルコールが前記低粘性溶媒１０重量部以上２２０重量部以下と前記高粘性アルコール２重量部以上５５重量部以下とを含むことが好ましい。
式（３）
　２．０重量％≦ＰＥＤＯＴ／ＰＳＳ水溶液＜３．０重量％ In the ink composition of the present invention, the concentration of the PEDOT / PSS aqueous solution satisfies the following relational expression (3), and the mixed alcohol is 10 parts by weight or more and 220 parts by weight or less of the low viscosity solvent and 2 parts by weight of the high viscosity alcohol. It is preferable that it contains 55 parts by weight or less.
Formula (3)
2.0 wt% ≦ PEDOT / PSS aqueous solution <3.0 wt%
　本発明のインク組成物においては、前記ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が下記関係式（４）を満たし、前記混合アルコールが前記低粘性溶媒５重量部以上２５０重量部以下と前記高粘性アルコール１重量部以上６５重量部以下とを含むことが好ましい。
式（４）
　３．０重量％≦ＰＥＤＯＴ／ＰＳＳ水溶液＜３．５重量％ In the ink composition of the present invention, the concentration of the PEDOT / PSS aqueous solution satisfies the following relational expression (4), and the mixed alcohol is 5 parts by weight or more and 250 parts by weight or less of the low viscosity solvent and 1 part by weight of the high viscosity alcohol. It is preferable that it contains 65 parts by weight or less.
Formula (4)
3.0 wt% ≦ PEDOT / PSS aqueous solution <3.5 wt%
　本発明のインク組成物の製造方法は、上記インク組成物の製造方法であって、前記ＰＥＤＯＴ／ＰＳＳ水溶液と、前記混合アルコールと、前記シランカップリング剤と、を含む溶液を撹拌してゲル化するゲル化工程と、ゲル化した前記溶液をインク化してインク組成物を製造するインク化工程と、を含むことを特徴とする。 The method for producing an ink composition of the present invention is a method for producing the ink composition, wherein the solution containing the PEDOT / PSS aqueous solution, the mixed alcohol, and the silane coupling agent is stirred to gel. And a gelation step of producing an ink composition by converting the gelled solution into an ink.
　この方法によれば、バインダーポリマーなどの増粘剤を加えることなく、ＰＥＤＯＴ／ＰＳＳ水溶液と、混合アルコールと、シランカップリング剤と、を含む溶液が適切なゲル化状態となる。そして、ゲル化した溶液をインク化することにより、インク組成物の粘度を適度な範囲とすることができるので、スクリーン印刷方式に適したインク組成物を製造することができる。そして、このインク組成物は、絶縁性のポリマーバインダーを含まずに粘度を上げていることから、導電率が高い透明導電膜を製造することが可能となる。 According to this method, a solution containing the PEDOT / PSS aqueous solution, the mixed alcohol, and the silane coupling agent becomes an appropriate gelation state without adding a thickener such as a binder polymer. Then, by converting the gelled solution into an ink, the viscosity of the ink composition can be adjusted to an appropriate range, so that an ink composition suitable for a screen printing method can be produced. And since this ink composition has increased viscosity without containing an insulating polymer binder, it becomes possible to produce a transparent conductive film having high conductivity.
　本発明の透明導電膜は、上記インク組成物を用いて形成されたことを特徴とする。 The transparent conductive film of the present invention is formed using the above ink composition.
　本発明の透明導電膜の製造方法は、上記インク組成物の製造方法によって製造されたインク組成物を用いることを特徴とする。 The method for producing a transparent conductive film of the present invention is characterized by using the ink composition produced by the method for producing an ink composition.
　本発明によれば、スクリーン印刷方式による透明導電膜の形成が可能であり、しかも導電率及び透過率に優れた透明導電膜が得られるインク組成物、インク組成物の製造方法、透明導電膜及び透明導電膜の製造方法を実現できる。 According to the present invention, an ink composition capable of forming a transparent conductive film by a screen printing method and obtaining a transparent conductive film excellent in conductivity and transmittance, a method for producing the ink composition, a transparent conductive film, and The manufacturing method of a transparent conductive film is realizable.
本実施の形態に係るインク組成物の概念図である。It is a conceptual diagram of the ink composition which concerns on this Embodiment. 本実施の形態に係るインク組成物におけるＰＥＤＯＴ／ＰＳＳの分子間の相互作用の説明図である。It is explanatory drawing of the interaction between the molecules of PEDOT / PSS in the ink composition which concerns on this Embodiment. 本実施の形態に係る透明導電膜の赤外吸収スペクトルを示す図である。It is a figure which shows the infrared absorption spectrum of the transparent conductive film which concerns on this Embodiment. 本実施の形態に係る透明導電膜の製造工程の概略を示すフロー図である。It is a flowchart which shows the outline of the manufacturing process of the transparent conductive film which concerns on this Embodiment.
　透明導電膜の形成に用いる導電性有機材料としては、ＰＥＤＯＴ／ＰＳＳ水溶液と、シランカップリング剤と、を含むインク組成物が挙げられる。このインク組成物は、絶縁性の各種ポリマーバインダーなどを加えて高粘度化することにより、製造コストに優れたスクリーン印刷による透明導電膜の形成が可能となる。一方で、絶縁性の各種ポリマーバインダーを添加した場合には、透明導電膜の膜厚を厚くする必要があり、透明導電膜の光の透過率の低下や透明導電膜による導電パターンの視認性の低下が問題となる。 Examples of the conductive organic material used for forming the transparent conductive film include an ink composition containing a PEDOT / PSS aqueous solution and a silane coupling agent. This ink composition can be formed into a transparent conductive film by screen printing with excellent production cost by adding various insulating polymer binders to increase the viscosity. On the other hand, when various insulating polymer binders are added, it is necessary to increase the film thickness of the transparent conductive film, which reduces the light transmittance of the transparent conductive film and the visibility of the conductive pattern by the transparent conductive film. Decrease is a problem.
　本発明者らは、所定量のＰＥＤＯＴ／ＰＳＳ水溶液と、所定量のシランカップリング剤と、所定量の混合アルコールと、を含む溶液においては、ＰＥＤＯＴ／ＰＳＳ水溶液が低濃度の領域においても適切なゲル化が進行することを見出した。そして、本発明者らは、この適切にゲル化した溶液をインク化してインク組成物とすることにより、各種ポリマーバインダーなどの増粘剤を用いずに、スクリーン印刷方式の透明導電膜の形成に適し、しかも導電率及び光透過性に優れたインク組成物を実現できることを見出し、本発明を完成させるに至った。 In the solution containing a predetermined amount of a PEDOT / PSS aqueous solution, a predetermined amount of a silane coupling agent, and a predetermined amount of mixed alcohol, the present inventors are suitable even in a region where the PEDOT / PSS aqueous solution has a low concentration. It was found that gelation proceeds. Then, the present inventors converted this appropriately gelled solution into an ink to form an ink composition, thereby forming a transparent conductive film for screen printing without using a thickener such as various polymer binders. The present inventors have found that an ink composition that is suitable and excellent in electrical conductivity and light transmittance can be realized, and has completed the present invention.
　以下、本発明の一実施の形態について、添付図面を参照して詳細に説明する。
　本発明に係るインク組成物は、ＰＥＤＯＴ／ＰＳＳ水溶液１００重量部と、混合アルコール３００重量部以下と、シランカップリング剤と、を混合した溶液をインク化してなり、前記ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が下記関係式（１）を満たし、前記混合アルコールが低粘性溶媒と高粘性アルコールとを含む。
式（１）
　１．３重量％≦ＰＥＤＯＴ／ＰＳＳ水溶液＜３．５重量％ Hereinafter, an embodiment of the present invention will be described in detail with reference to the accompanying drawings.
The ink composition according to the present invention is an ink composition obtained by mixing 100 parts by weight of an aqueous PEDOT / PSS solution, 300 parts by weight or less of a mixed alcohol, and a silane coupling agent. The following relational expression (1) is satisfied, and the mixed alcohol includes a low viscosity solvent and a high viscosity alcohol.
Formula (1)
1.3 wt% ≦ PEDOT / PSS aqueous solution <3.5 wt%
　本発明に係るインク組成物によれば、低粘性溶媒と高粘性アルコールとを含む混合アルコールを所定量含有することから、所定量のＰＥＤＯＴ／ＰＳＳ水溶液、所定量の混合アルコール及びシランカップリング剤を含む溶液の適切なゲル化の濃度範囲が低濃度側にシフトする。これにより、ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が上記式（１）を満たす範囲で適切なゲル化状態となるので、増粘剤としての各種ポリマーバインダーを添加することなく、インク組成物がスクリーン印刷に適した高粘度溶液となる。そして、非導電性の各種ポリマーバインダーを添加することなくスクリーン印刷が可能となるので、インク組成物から得られた透明導電膜の膜厚の増大を防ぐことが可能となると共に、絶縁抵抗の増大を防ぐことができる。この結果、絶縁抵抗値に優れた透明導電膜を実現することができる。 According to the ink composition of the present invention, since a predetermined amount of mixed alcohol containing a low-viscosity solvent and a high-viscosity alcohol is contained, a predetermined amount of PEDOT / PSS aqueous solution, a predetermined amount of mixed alcohol, and a silane coupling agent are added. The concentration range of the appropriate gelation of the contained solution is shifted to the lower concentration side. As a result, the PEDOT / PSS aqueous solution is in an appropriate gelation state within a range satisfying the above formula (1), so that the ink composition is suitable for screen printing without adding various polymer binders as a thickener. A highly viscous solution. Since screen printing can be performed without adding various non-conductive polymer binders, it is possible to prevent an increase in the thickness of the transparent conductive film obtained from the ink composition and increase the insulation resistance. Can be prevented. As a result, a transparent conductive film having an excellent insulation resistance value can be realized.
　なお、本発明に係るインク組成物において、「適切なゲル化状態」とは、所定量のＰＥＤＯＴ／ＰＳＳ水溶液、所定量の混合アルコール及びシランカップリング剤を含む溶液がゲル化した状態及び高粘度溶液の状態のいずれも含むものとする。ゲル化した状態としては、溶液の一部がゲル化した状態であってもよく、溶液の全てがゲル化して固化した状態であってもよい。 In the ink composition according to the present invention, “appropriate gelation state” means a state in which a solution containing a predetermined amount of PEDOT / PSS aqueous solution, a predetermined amount of mixed alcohol and a silane coupling agent is gelled, and high viscosity. Any solution state shall be included. The gelled state may be a state where a part of the solution is gelled, or may be a state where all of the solution is gelled and solidified.
　図１は、本発明に係るインク組成物の概念図である。本発明に係るインク組成物においては、導電性高分子化合物としてのＰＥＤＯＴ１１との高分子電荷移動錯体としてのＰＳＳ１２との間にバインダーとしてのシランカップリング剤１３によって架橋結合（クロスリンク）が形成される。この架橋結合により、ＰＥＤＯＴ１１とＰＳＳ１２とを含む導電性化合物の間にシランカップリング剤を介した３次元的なネットワークが形成されるので、インク組成物を用いて形成される透明導電膜の膜強度が向上する。 FIG. 1 is a conceptual diagram of an ink composition according to the present invention. In the ink composition according to the present invention, a cross-link is formed by the silane coupling agent 13 as a binder between the PEDOT 11 as a conductive polymer compound and the PSS 12 as a polymer charge transfer complex. The By this cross-linking, a three-dimensional network through a silane coupling agent is formed between the conductive compounds including PEDOT11 and PSS12, so that the film strength of the transparent conductive film formed using the ink composition Will improve.
　ここで、本発明に係るインク組成物においては、ＰＥＤＯＴ／ＰＳＳ水溶液が上記式（１）を満たすと共に、所定量の混合アルコールを含むことから、ＰＥＤＯＴ／ＰＳＳが適度に分散される共に、上記３次元的なネットワーク間に混合アルコール分子が侵入して適切なゲル化状態となる。この適切なゲル化状態により、インク組成物の粘度が適度に向上できるので、スクリーン印刷方式による透明導電膜の形成に必要な程度にインク組成物を高粘度化できる。これにより、透明導電膜の膜厚を増大させずに透明導電膜に必要な導電率を確保できるので、透明導電膜の透過率及び透明導電膜によって形成された導電パターンの視認性を低下させることが可能となる。 Here, in the ink composition according to the present invention, since the PEDOT / PSS aqueous solution satisfies the above formula (1) and contains a predetermined amount of mixed alcohol, the PEDOT / PSS is appropriately dispersed and the above 3 The mixed alcohol molecules enter between the dimensional networks to form an appropriate gel state. Since the viscosity of the ink composition can be appropriately improved by this appropriate gelation state, the viscosity of the ink composition can be increased to an extent necessary for forming a transparent conductive film by a screen printing method. As a result, the necessary conductivity of the transparent conductive film can be ensured without increasing the film thickness of the transparent conductive film, thereby reducing the transmittance of the transparent conductive film and the visibility of the conductive pattern formed by the transparent conductive film. Is possible.
　まず、本発明者らは、本発明に係るインク組成物の適切なゲル化状態の痕跡について詳細に調べた。図２は、本発明に係るインク組成物におけるＰＥＤＯＴ／ＰＳＳの分子間の相互作用の説明図であり、図３は、本発明に係る透明導電膜の赤外吸収スペクトルを示す図である。 First, the present inventors examined in detail the trace of the appropriate gelation state of the ink composition according to the present invention. FIG. 2 is an explanatory diagram of the interaction between molecules of PEDOT / PSS in the ink composition according to the present invention, and FIG. 3 is a diagram showing an infrared absorption spectrum of the transparent conductive film according to the present invention.
　図２に示すように、本発明に係るインク組成物においては、ＰＥＤＯＴ分子２１とＰＳＳ分子２２との間に硫黄原子を介した相互作用（図２の点線参照）が生じている。これはＰＳＳ分子２２によるＰＥＤＯＴ分子２１のドーピング状態を表し、ＰＥＤＯＴ分子２１に正電荷が供給され、これがホールキャリアのポーラロンやバイポーラロンとなる。図１に示したＰＳＳ１２に沿ってＰＥＤＯＴ１１が配置されている状態がこれに対応する。一方、高粘度溶液に出来る適切なゲル化の状態は、主にイオン性高分子のＰＳＳ分子２２が所定の割合で添加される低粘性溶媒や高粘性アルコールの存在下で、クーロン相互作用による近距離秩序が形成されている状態である。 As shown in FIG. 2, in the ink composition according to the present invention, an interaction via sulfur atoms occurs between the PEDOT molecule 21 and the PSS molecule 22 (see the dotted line in FIG. 2). This represents a doping state of the PEDOT molecule 21 by the PSS molecule 22, and a positive charge is supplied to the PEDOT molecule 21, which becomes a hole carrier polaron or bipolaron. The state where the PEDOT 11 is arranged along the PSS 12 shown in FIG. 1 corresponds to this. On the other hand, an appropriate gelation state that can be obtained in a high-viscosity solution is the proximity due to Coulomb interaction mainly in the presence of a low-viscosity solvent or high-viscosity alcohol to which PSS molecules 22 of an ionic polymer are added at a predetermined ratio. This is a state where distance order is formed.
　このようにして形成された近距離秩序により、図３のゲル化処理をする前のインク組成物を塗布して形成した透明導電膜の赤外吸収スペクトルを示す実線Ｌ１に対して、Ｌ２及びＬ３に示すように、ゲル化後に攪拌処理を行ったインク組成物を塗布して形成した透明導電膜の赤外吸収スペクトルにおいて、スルホン酸基に基づくピーク（１０８７ｃｍ－１、１２０３ｃｍ－１、１３０９ｃｍ－１、１５２３ｃｍ－１）の強度が変化する。また、この近距離秩序は、インク組成物の撹拌処理の強度によって変化し、撹拌処理を強く行った場合（図３の実線Ｌ３）に対して、撹拌処理を弱く行った場合は、スルホン酸基に基づくピークの強度が相対的に小さくなることが分かる。これらの結果から、本発明に係るインク組成物においては、撹拌処理の前後でゲル化が生じていることが分かる。 L2 and L3 with respect to the solid line L1 indicating the infrared absorption spectrum of the transparent conductive film formed by applying the ink composition before the gelation treatment in FIG. As shown in the graph, in the infrared absorption spectrum of the transparent conductive film formed by applying the ink composition subjected to the stirring treatment after gelation, peaks based on sulfonic acid groups (1087 cm −1 , 1203 cm −1 , 1309 cm −1). , 1523 cm −1 ). Further, this short-range order changes depending on the strength of the stirring process of the ink composition. When the stirring process is performed strongly (solid line L3 in FIG. 3), when the stirring process is performed weakly, the sulfonic acid group It can be seen that the intensity of the peak based on is relatively small. From these results, it can be seen that gelation occurs in the ink composition according to the present invention before and after the stirring treatment.
　次に、本実施の形態に係るインク組成物に用いられる材料について詳細に説明する。 Next, materials used for the ink composition according to the present embodiment will be described in detail.
　ＰＥＤＯＴ／ＰＳＳ水溶液としては、上記式（１）に示す濃度範囲を満たすものであれば、本発明の効果を奏する範囲で各種ＰＥＤＯＴ／ＰＳＳ水溶液を用いることができる。このＰＥＤＯＴ／ＰＳＳとしては、市販品をそのまま用いてもよい。ＰＥＤＯＴ／ＰＳＳ水溶液の市販品としては、例えば、Ｃｌｅｖｉｏｓ（登録商標：Ｈｅｒａｅｕｓ社製）　Ｐ、Ｃｌｅｖｉｏｓ　ＰＨ５００、Ｃｌｅｖｉｏｓ　ＰＨ１０００などが挙げられる。 As the PEDOT / PSS aqueous solution, various PEDOT / PSS aqueous solutions can be used as long as the concentration range shown in the above formula (1) is satisfied. As this PEDOT / PSS, you may use a commercial item as it is. Examples of commercially available PEDOT / PSS aqueous solutions include Clevios (registered trademark: manufactured by Heraeus) P, Clevios PH500, and Clevios PH1000.
　シランカップリング剤としては、バインダーとして用いることができるものであれば、本発明の効果を奏する範囲で各種シランカップリング剤を用いることができる。シランカップリング剤としては、例えば、エポキシ基を含有するジアルコキシシランや、エポキシ基を含有するトリアルコキシシランなどを用いることができる。エポキシ基を含有するジエポキシシランとしては、例えば、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルメチルジエトキシシランなどを用いることができる。また、エポキシ基を含有するトリエポキシシランとしては、例えば、３－グリシドキシプロピルトリメトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリエトキシシランなどが挙げられる。 As the silane coupling agent, various silane coupling agents can be used as long as they can be used as a binder within the scope of the effects of the present invention. As the silane coupling agent, for example, dialkoxysilane containing an epoxy group, trialkoxysilane containing an epoxy group, and the like can be used. As the diepoxysilane containing an epoxy group, for example, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and the like can be used. Examples of the triepoxysilane containing an epoxy group include 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl). Examples thereof include ethyltriethoxysilane.
　混合アルコールとしては、低粘性溶媒と高粘性アルコールとを混合したものを用いる。ここで、低粘性溶媒とは、粘性が２．５ｃｐ未満のものであり、高粘性アルコールとは、粘性が２０ｃｐ以上ものである。低粘性溶媒としては、本発明の効果を奏する範囲であれば特に制限はない。 As the mixed alcohol, a mixture of a low viscosity solvent and a high viscosity alcohol is used. Here, the low viscosity solvent has a viscosity of less than 2.5 cp, and the high viscosity alcohol has a viscosity of 20 cp or more. The low viscosity solvent is not particularly limited as long as the effects of the present invention are achieved.
　混合アルコールは、ＰＥＤＯＴ／ＰＳＳ水溶液１００重量部に対して、３００重量部以下である。これにより、インク組成物を適切にゲル化させることが可能となる。また、混合アルコールは、ＰＥＤＯＴ／ＰＳＳ水溶液１００重量部に対して、１００重量部以上３００重量部以下の範囲内であることが好ましい。 The mixed alcohol is 300 parts by weight or less with respect to 100 parts by weight of the PEDOT / PSS aqueous solution. Thereby, the ink composition can be appropriately gelled. Moreover, it is preferable that mixed alcohol exists in the range of 100 to 300 weight part with respect to 100 weight part of PEDOT / PSS aqueous solution.
　低粘性溶媒としては、低級アルコールを用いることが好ましい。低級アルコールとしては、例えば、メタノール、エタノール又はプロパノールなどが好ましい。この低級アルコールを用いることにより、適切なゲル化状態を容易に得ることができる。なお、プロパノールとしては、１－プロパノールを用いてもよく、２－プロパノール（イソプロパノール）を用いてもよい。 It is preferable to use a lower alcohol as the low viscosity solvent. As the lower alcohol, for example, methanol, ethanol or propanol is preferable. By using this lower alcohol, an appropriate gelled state can be easily obtained. As propanol, 1-propanol or 2-propanol (isopropanol) may be used.
　また、低粘性溶媒としては、グリコールモノアルキルエーテルを用いることも好ましい。グリコールモノアルキルエーテルは、グリコールの一方の水酸基がエーテル化されたものであり、一方の水酸基が残存していることから、アルコールに近い特性を有するので、低級アルコールと同様の効果を得ることができる。グリコールモノアルキルエーテルとしては、例えば、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）やジエチレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテルなどが挙げられる。 It is also preferable to use glycol monoalkyl ether as the low viscosity solvent. Glycol monoalkyl ether is one in which one hydroxyl group of glycol is etherified, and since one hydroxyl group remains, it has characteristics close to that of alcohol, so the same effect as lower alcohol can be obtained. . Examples of the glycol monoalkyl ether include propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, and ethylene glycol monomethyl ether.
　高粘性アルコールとしては、本発明の効果を奏する範囲であれば特に制限はない。高粘性アルコールとしては、例えば、各種ジオール化合物（各種グリコール）を用いることができる。これらの中でも、高粘性アルコールとしては、エチレングリコール、プロピレングリコール、ブタンジオール又はジエチレングリコールを用いることが好ましく、プロピレングリコール又はブタンジオールであることがより好ましい。 The high-viscosity alcohol is not particularly limited as long as it has the effects of the present invention. As the highly viscous alcohol, for example, various diol compounds (various glycols) can be used. Among these, as the high viscosity alcohol, it is preferable to use ethylene glycol, propylene glycol, butanediol, or diethylene glycol, and more preferable is propylene glycol or butanediol.
　また、本発明に係るインク組成物においては、本発明の効果を奏する範囲でエンハンサーとしての高粘性溶媒を用いてもよい。このような高粘性化合物としては、例えば、ジメチルスルホキシド（ＤＭＳＯ）などが挙げられる。 In the ink composition according to the present invention, a highly viscous solvent as an enhancer may be used as long as the effects of the present invention are achieved. Examples of such highly viscous compounds include dimethyl sulfoxide (DMSO).
　次に、本発明者らは、インク組成物の組成とゲル化との関係について詳細に調べた。ここでは、下記表１を参照しながら、市販品のＰＥＤＯＴ／ＰＳＳ水溶液（商品名：Ｃｌｅｖｉｏｓ（登録商標）Ｐ（濃度１．８重量％））を使用し、水による希釈や加熱濃縮によってＰＥＤＯＴ／ＰＳＳの濃度を変化させた場合のＰＥＤＯＴ／ＰＳＳ濃度及び混合アルコール（アルコールとグリコール）の組成と適切なゲル化状態との関係について説明する。なお、以下の例では、シランカップリング剤は、ＰＥＤＯＴ／ＰＳＳの固形分と等量用いている。また、混合アルコールとしては、低粘性溶媒としてのイソプロパノール（ＩＰＡ）と高粘性アルコールとしてのプロピレングリコール（ＰＧ）との混合比（ＩＰＡ：ＰＧ）を４：１として混合アルコールの量を変化させた場合と、ＰＥＤＯＴ／ＰＳＳ水溶液１００重量部に対して混合アルコールの総量を３００重量部として低粘性溶媒と高粘性アルコールとの組成比を変化させている。 Next, the present inventors examined in detail the relationship between the composition of the ink composition and gelation. Here, referring to Table 1 below, a commercially available PEDOT / PSS aqueous solution (trade name: Clevios (registered trademark) P (concentration 1.8% by weight)) was used, and PEDOT / PSD was diluted by water or concentrated by heating. The relationship between the PEDOT / PSS concentration and the composition of the mixed alcohol (alcohol and glycol) and the appropriate gelation state when the PSS concentration is changed will be described. In the following examples, the silane coupling agent is used in an amount equivalent to the solid content of PEDOT / PSS. In addition, as the mixed alcohol, the amount of the mixed alcohol is changed by setting the mixing ratio (IPA: PG) of isopropanol (IPA) as the low viscosity solvent and propylene glycol (PG) as the high viscosity alcohol to 4: 1. The composition ratio of the low-viscosity solvent and the high-viscosity alcohol is changed by setting the total amount of the mixed alcohol to 300 parts by weight with respect to 100 parts by weight of the PEDOT / PSS aqueous solution.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　上記表１に示すように、本発明に係るインク組成物においては、用いるＰＥＤＯＴ／ＰＳＳ水溶液の濃度を１．３重量％以上の範囲とすることにより、インク組成物を混合して適切にゲル化状態にすることが可能となる。また、用いるＰＥＤＯＴ／ＰＳＳ水溶液の濃度を３．５以下とすることにより、溶液全体の固化を防ぐことが可能となり、インク組成物を濃縮して回収することが可能となる。 As shown in Table 1 above, in the ink composition according to the present invention, the concentration of the PEDOT / PSS aqueous solution to be used is in the range of 1.3% by weight or more, so that the ink composition is mixed and appropriately gelled. It becomes possible to be in a state. Further, by setting the concentration of the aqueous PEDOT / PSS solution to be 3.5 or less, it is possible to prevent solidification of the entire solution, and it is possible to concentrate and collect the ink composition.
　まず、混合アルコールの組成を低粘性溶媒（ＩＰＡ）：高粘性アルコール（ＰＧ）＝４：１とした場合について説明する。この場合、ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が大きくなるにつれて低粘性の低級アルコールの量を少なくしても適正なゲル化状態にすることが可能となる。この結果は、適正なゲル化状態になるためのイオン性高分子、主にＰＳＳの濃度が高い為、少量の低粘性の低級アルコールでも可能となると考えられる。 First, the case where the composition of the mixed alcohol is low viscosity solvent (IPA): high viscosity alcohol (PG) = 4: 1 will be described. In this case, even if the amount of the low-viscosity lower alcohol is decreased as the concentration of the aqueous solution of PEDOT / PSS increases, an appropriate gelled state can be obtained. This result is considered to be possible even with a small amount of a low-viscosity lower alcohol because the concentration of the ionic polymer for achieving an appropriate gelation state, mainly PSS, is high.
　ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が下記関係式（２）を満たす場合には、混合アルコールが低粘性溶媒１００重量部以上１５０重量部以下と高粘性アルコール２００重量部以上１５０重量部以下とを含む範囲でゲル化させることができる。
式（２）
　１．３重量％≦ＰＥＤＯＴ／ＰＳＳ水溶液＜２．０重量％ When the concentration of the PEDOT / PSS aqueous solution satisfies the following relational expression (2), the mixed alcohol contains 100 to 150 parts by weight of the low-viscosity solvent and 200 to 150 parts by weight of the high-viscosity alcohol. It can be gelled.
Formula (2)
1.3 wt% ≦ PEDOT / PSS aqueous solution <2.0 wt%
　また、ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が下記関係式（３）を満たす場合には、混合アルコールが低粘性溶媒１５重量部以上１８０重量部以下と高粘性アルコール２８５重量部以上１２０重量部以下とを含む範囲でゲル化させることができる。
式（３）
　２．０重量％≦ＰＥＤＯＴ／ＰＳＳ水溶液＜３．０重量％ Moreover, when the density | concentration of PEDOT / PSS aqueous solution satisfy | fills the following relational expression (3), mixed alcohol contains 15 to 180 weight part of low-viscosity solvent and 285 to 120 weight part of high-viscosity alcohol. It can be gelled in a range.
Formula (3)
2.0 wt% ≦ PEDOT / PSS aqueous solution <3.0 wt%
　さらに、ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が下記関係式（４）を満たす場合には、混合アルコールが低粘性溶媒１０重量部以上２００重量部以下と高粘性アルコール２９０重量部以上１００重量部以下とを含む範囲でゲル化させることができる。
式（４）
　３．０重量％≦ＰＥＤＯＴ／ＰＳＳ水溶液＜３．５重量％ Further, when the concentration of the aqueous solution of PEDOT / PSS satisfies the following relational expression (4), the mixed alcohol includes 10 to 200 parts by weight of the low-viscosity solvent and 290 to 100 parts by weight of the high-viscosity alcohol. It can be gelled in a range.
Formula (4)
3.0 wt% ≦ PEDOT / PSS aqueous solution <3.5 wt%
　次に、ＰＥＤＯＴ／ＰＳＳ水溶液１００重量部に対して混合アルコール３００重量部を用いた場合について説明する。この場合、用いるＰＥＤＯＴ／ＰＳＳ水溶液の濃度が高くなるにつれて低粘性溶媒の割合を小さくしてもインク組成物を適正にゲル化状態にすることができる。この結果は、適正なゲル化状態になる為のイオン性高分子、主にＰＳＳの濃度が高いため、少量の低粘性の低級アルコールでも可能となるためと考えられる。 Next, the case where 300 parts by weight of mixed alcohol is used with respect to 100 parts by weight of the PEDOT / PSS aqueous solution will be described. In this case, even if the ratio of the low-viscosity solvent is decreased as the concentration of the aqueous PEDOT / PSS solution to be used is increased, the ink composition can be appropriately gelled. This result is considered to be possible because even a small amount of a low-viscosity lower alcohol is possible because the concentration of the ionic polymer for achieving an appropriate gelation state, mainly PSS, is high.
　ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が下記関係式（２）を満たす場合には、混合アルコールが低粘性溶媒８０重量部以上２００重量部以下と高粘性アルコール２０重量部以上５０重量部以下とを含む範囲で適正なゲル化状態にさせることが可能となる。
式（２）
　１．３重量％≦ＰＥＤＯＴ／ＰＳＳ水溶液＜２．０重量％ When the concentration of the PEDOT / PSS aqueous solution satisfies the following relational expression (2), the mixed alcohol contains 80 to 200 parts by weight of the low-viscosity solvent and 20 to 50 parts by weight of the high-viscosity alcohol. It becomes possible to make it an appropriate gelation state.
Formula (2)
1.3 wt% ≦ PEDOT / PSS aqueous solution <2.0 wt%
　また、ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が下記関係式（３）を満たす場合には、混合アルコールが低粘性溶媒１０重量部以上２２０重量部以下と高粘性グリコール２重量部以上５５重量部以下とを含む範囲で適正にゲル化状態にさせることが可能となる。
式（３）
　２．０重量％≦ＰＥＤＯＴ／ＰＳＳ水溶液＜３．０重量％ Moreover, when the density | concentration of PEDOT / PSS aqueous solution satisfy | fills the following relational expression (3), mixed alcohol contains 10 to 220 weight part of low-viscosity solvent and 2 to 55 weight part or less of high-viscosity glycol. It becomes possible to make it a gelation state appropriately in the range.
Formula (3)
2.0 wt% ≦ PEDOT / PSS aqueous solution <3.0 wt%
　さらに、ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が下記関係式（４）を満たす場合には、混合アルコールが低粘性溶媒５重量部以上２５０重量部以下と高粘性アルコール１重量部以上６５重量部以下とを含む範囲で適正なゲル化状態にさせることが可能となる。
式（４）
　３．０重量％≦ＰＥＤＯＴ／ＰＳＳ水溶液＜３．５重量％ Further, when the concentration of the aqueous solution of PEDOT / PSS satisfies the following relational expression (4), the mixed alcohol includes 5 to 250 parts by weight of the low-viscosity solvent and 1 to 65 parts by weight of the high-viscosity alcohol. It becomes possible to make it an appropriate gelation state in the range.
Formula (4)
3.0 wt% ≦ PEDOT / PSS aqueous solution <3.5 wt%
　このように、本発明に係るインク組成物においては、ＰＥＤＯＴ／ＰＳＳ水溶液を上記関係式（１）を満たす範囲とすることにより、混合アルコールの組成及び総量に関して広い範囲でインク組成物を適正なゲル化状態にさせることが可能となる。これにより、非導電性の各種バインダーポリマーを用いることなく、インク組成物の粘度をスクリーン印刷に適した範囲にすることができるので、導電性及び透過率に優れた透明導電膜をえることが可能となる。 Thus, in the ink composition according to the present invention, by setting the PEDOT / PSS aqueous solution in a range that satisfies the above relational expression (1), the ink composition can be appropriately gel in a wide range with respect to the composition and total amount of the mixed alcohol. It becomes possible to make it into a conversion state. As a result, the viscosity of the ink composition can be made suitable for screen printing without using various non-conductive binder polymers, so that it is possible to obtain a transparent conductive film excellent in conductivity and transmittance. It becomes.
　次に、本発明に係るインク組成物の製造方法について説明する。図４は、本実施の形態に係る透明導電膜の製造工程の概略を示すフロー図である。本発明に係るインクの製造方法は、ＰＥＤＯＴ／ＰＳＳ水溶液と、混合アルコールと、シランカップリング剤と、を混合してゲル化するゲル化工程と、このゲルをインク化してインク組成物を製造するインク化工程と、を含む。 Next, a method for producing the ink composition according to the present invention will be described. FIG. 4 is a flowchart showing an outline of the manufacturing process of the transparent conductive film according to the present embodiment. The method for producing an ink according to the present invention includes a gelling step in which a PEDOT / PSS aqueous solution, a mixed alcohol, and a silane coupling agent are mixed to form a gel, and an ink composition is manufactured by converting the gel into an ink. An inking process.
　ゲル化工程においては、上述したＰＥＤＯＴ／ＰＳＳ原液（ＰＥＤＯＴ／ＰＳＳのみを含む水溶液）にエンハンサーとしてのＤＭＳＯ（ジメチルスルホキシド）、ＰＥＤＯＴ：ＰＳＳの固形分と等量のシランカップリング剤、及び所定の組成を有する混合アルコールを添加してＰＥＤＯＴ／ＰＳＳ水溶液を調合する（ＳＴ１、ＳＴ２）。そして、このＰＥＤＯＴ／ＰＳＳ水溶液を所定時間の撹拌・混合した後、撹拌を停止して数時間から１晩放置することにより混合溶液を適切なゲル化状態にさせる（ＳＴ３、ＳＴ４）。次に、インク化工程においては、ゲル化状態の溶液を約１時間撹拌してインク化し、インク組成物を製造する（ＳＴ５）。 In the gelation step, DMSO (dimethyl sulfoxide) as an enhancer in the above PEDOT / PSS stock solution (aqueous solution containing only PEDOT / PSS), a silane coupling agent equivalent to the solid content of PEDOT: PSS, and a predetermined composition PEDOT / PSS aqueous solution is prepared by adding mixed alcohol having (ST1, ST2). And after stirring and mixing this PEDOT / PSS aqueous solution for a predetermined time, stirring is stopped and it is left to stand for several hours to overnight, and let a mixed solution be a suitable gelled state (ST3, ST4). Next, in the ink forming step, the gelled solution is stirred for about 1 hour to make ink, thereby producing an ink composition (ST5).
　本発明に係るインク組成物の製造方法によれば、バインダーポリマーなどの増粘剤を加えることなく、ゲル化によりインク組成物の粘度を適度な範囲とすることができるので、スクリーン印刷に適した高粘度（１００ｃｐ以上：撹拌速度５ｒｐｍ）インク組成物を製造することができる。そして、このインク組成物は、絶縁性のポリマーバインダーを含まずに粘度を上げていることから、導電率が高い透明導電膜を製造することが可能となる。 According to the method for producing an ink composition according to the present invention, the viscosity of the ink composition can be adjusted to an appropriate range by gelation without adding a thickener such as a binder polymer, which is suitable for screen printing. An ink composition having a high viscosity (100 cp or more: stirring speed 5 rpm) can be produced. And since this ink composition has increased viscosity without containing an insulating polymer binder, it becomes possible to produce a transparent conductive film having high conductivity.
　以上説明したように、上記実施の形態に係るインク組成物によれば、低粘性溶媒と高粘性アルコールとを含む混合アルコールを所定量含有することから、所定量のＰＥＤＯＴ／ＰＳＳ水溶液、所定量の混合アルコール及びシランカップリング剤を含む溶液の適切なゲル化状態の濃度範囲が低濃度側にシフトするので、ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が上記式（１）を満たす範囲で適切なゲル状態となる。この適切なゲル状態とすることにより、インク組成物の粘度がスクリーン印刷に適した範囲となるので、増粘剤としての各種ポリマーバインダーを添加する必要がない。これにより、スクリーン印刷やディスペンサーによる塗布に対応することが可能となる。また、高濃度バインダーの添加や高粘度溶媒を用いずにインク組成物を高粘度化できるので、インク組成物を用いて得られる透明導電膜の低抵抗化及び耐久性を向上できる。また、低温での焼成（例えば、１１０℃以下、２０分）することが可能となる。 As described above, the ink composition according to the above embodiment contains a predetermined amount of mixed alcohol containing a low-viscosity solvent and a high-viscosity alcohol, so that a predetermined amount of PEDOT / PSS aqueous solution, a predetermined amount of Since the concentration range of the appropriate gelation state of the solution containing the mixed alcohol and the silane coupling agent shifts to the low concentration side, the gel state is in an appropriate range as long as the concentration of the aqueous solution of PEDOT / PSS satisfies the above formula (1). . By setting it to this appropriate gel state, the viscosity of the ink composition falls within a range suitable for screen printing, so there is no need to add various polymer binders as thickeners. Thereby, it becomes possible to cope with application by screen printing or a dispenser. Moreover, since the viscosity of the ink composition can be increased without using a high-concentration binder or a high-viscosity solvent, the resistance and durability of the transparent conductive film obtained using the ink composition can be improved. Moreover, it becomes possible to perform baking at a low temperature (for example, 110 ° C. or less, 20 minutes).
　次に、本発明の効果を明確にするために行った実施例について説明する。なお、本発明は、以下の実施例によって限定されるものではない。 Next, examples carried out to clarify the effects of the present invention will be described. The present invention is not limited to the following examples.
　以下の実施例においては、本実施の形態に係るインク組成物及び比較例に係るインク組成物を作製し、作製したインク組成物の特性について評価した。また、作製したインク組成物を用いて透明導電膜を作製し、その物性について評価した。以下に、各種物性測定条件を示す。 In the following examples, the ink composition according to the present embodiment and the ink composition according to the comparative example were produced, and the characteristics of the produced ink compositions were evaluated. Moreover, the transparent conductive film was produced using the produced ink composition, and the physical property was evaluated. Below, various physical property measurement conditions are shown.
（インク組成物のゲル化）
　インク組成物の適正なゲル化状態は、粘度計にて測定した粘度により判断した。 (Gelation of ink composition)
The proper gelation state of the ink composition was judged by the viscosity measured with a viscometer.
（粘度の測定）
　粘度は、コーン回転式粘度測定器（商品名レオメータ・粘度計、ハーケ社製）ＲｏｔｏＶｉｓｃｏ　１を用いてコーン回転速度５ｒｐｍの条件にて測定した。 (Measurement of viscosity)
The viscosity was measured using a cone rotation type viscosity measuring device (trade name rheometer / viscosimeter, manufactured by HAAKE) RotoVisco 1 under the condition of a cone rotation speed of 5 rpm.
（面積抵抗）
　透明導電膜の面積抵抗は、透明導電膜の表面抵抗を４探針式面積抵抗計（三菱化学社製、ＬＯＲＥＳＴＡ　ＥＰ　ＭＣＰ－１３６０）を用いて測定した面積抵抗（シート抵抗値）を用いた。 (Area resistance)
The sheet resistance of the transparent conductive film was the sheet resistance (sheet resistance value) obtained by measuring the surface resistance of the transparent conductive film using a four-probe type area resistance meter (LORESTA EP MCP-1360, manufactured by Mitsubishi Chemical Corporation).
（導電率）
　導電率は、面積抵抗値と膜厚の積で求めた。膜厚は、接触式段差計（ＤＥＫＴＡＫ）を用いてスクリーン印刷パターンの段差部を測定した。 (conductivity)
The conductivity was determined by the product of the sheet resistance value and the film thickness. The film thickness was measured on the step portion of the screen printing pattern using a contact type step meter (DEKTAK).
（全光線透過率）及び（ヘイズ）
　透明導電膜の全光線透過率及びヘイズは、ヘイズメータ（商品名ＨＺ－２、スガ試験機社製）を用いて測定した。全光線透過率は、ＪＩＳ－Ｋ７３６１－１、また、ヘイズは、ＪＩＳ－Ｋ７１３６に基づく計測を実施した。 (Total light transmittance) and (Haze)
The total light transmittance and haze of the transparent conductive film were measured using a haze meter (trade name HZ-2, manufactured by Suga Test Instruments Co., Ltd.). The total light transmittance was measured based on JIS-K7361-1, and haze was measured based on JIS-K7136.
　まず、本発明者らは、シランカップリング剤を一定量とした条件でＰＥＤＯＴ及び混合アルコール溶液の組成比とを変化させてインク組成物を作製し、作製したインク組成物を用いて得られた透明導電膜の物性について調べた（実施例１～実施例３、比較例１及び比較例２）。 First, the present inventors prepared an ink composition by changing the composition ratio of PEDOT and a mixed alcohol solution under the condition that the silane coupling agent was a constant amount, and the ink composition was obtained using the prepared ink composition. The physical properties of the transparent conductive film were examined (Example 1 to Example 3, Comparative Example 1 and Comparative Example 2).
＜実施例１＞
（インク組成物の調合）
　ＰＥＤＯＴ／ＰＳＳ水溶液としては、固形分の濃度が１．８重量％の市販品（Ｃｌｅｖｉｏｓ　Ｐ、Ｈｅｒａｅｕｓ社製）を用いた。このＰＥＤＯＴ／ＰＳＳ水溶液にＰＥＤＯＴ／ＰＳＳ固形分と等量のシランカップリング剤を添加した水溶液を調製した。この水溶液１００重量部に、混合アルコール１００重量部（イソプロパノール（８０重量部）：プロピレングリコール（２０重量部））及びエンハンサーとしてのジメチルスルホキシド（ＤＭＳＯ）１０重量部を添加して２２℃の条件下、１時間撹拌してインク組成物を作製した。次に、撹拌を停止して２間放置したところ、インク組成物が適正なゲル化状態となった。次に、ゲル化した溶液を２２℃の条件下、１時間撹拌したインク化してインク組成物を作製し、作製したインク組成物の粘度を測定したところ、粘度は５４０ｃｐであった。結果を下記表２に示す。 <Example 1>
(Preparation of ink composition)
As the PEDOT / PSS aqueous solution, a commercial product (Clevios P, manufactured by Heraeus) having a solid content of 1.8% by weight was used. An aqueous solution was prepared by adding an equivalent amount of a silane coupling agent to the PEDOT / PSS solid content to this PEDOT / PSS aqueous solution. To 100 parts by weight of this aqueous solution, 100 parts by weight of mixed alcohol (isopropanol (80 parts by weight): propylene glycol (20 parts by weight)) and 10 parts by weight of dimethyl sulfoxide (DMSO) as an enhancer were added. The ink composition was prepared by stirring for 1 hour. Next, stirring was stopped and the ink composition was allowed to stand for 2 hours. As a result, the ink composition became an appropriate gelled state. Next, the gelled solution was converted into an ink that was stirred for 1 hour at 22 ° C. to prepare an ink composition. The viscosity of the prepared ink composition was measured, and it was found to be 540 cp. The results are shown in Table 2 below.
（透明導電膜の作製）
　市販のスクリーン印刷版（テトロン材３５５メッシュ、メッシュ工業社製）を用いて、スクリーン印刷によりフィルム基材（ＰＥＴフィルム：厚み１００μｍ、１００ｍｍ四方）上にインク組成物を塗布して薄膜を形成した。スクリーン印刷の状態は、良好であった。 (Preparation of transparent conductive film)
Using a commercially available screen printing plate (Tetron material 355 mesh, manufactured by Mesh Kogyo Co., Ltd.), the ink composition was applied onto a film substrate (PET film: thickness 100 μm, 100 mm square) by screen printing to form a thin film. The state of screen printing was good.
　次に、得られた薄膜を１２０℃で２０分間ベークした。得られた透明導電膜は、膜厚が８６０ｎｍであり、面積抵抗が３７０Ω／□であり、導電率が３１Ｓ／ｃｍであり、全光線透過率が８３．２％、ヘイズが１．０であった。結果を下記表３に示す。 Next, the obtained thin film was baked at 120 ° C. for 20 minutes. The obtained transparent conductive film had a film thickness of 860 nm, a sheet resistance of 370 Ω / □, a conductivity of 31 S / cm, a total light transmittance of 83.2%, and a haze of 1.0. It was. The results are shown in Table 3 below.
＜実施例２＞
（インク組成物の調整）
　ジメチルスルホキシドの添加量を１５重量部とし、混合アルコールを２００重量部（イソプロパノール（１６０重量部）：プロピレングリコール（４０重量部））としたこと以外は、実施例１と同様にしてインク組成物を作製した。このインク組成物は、実施例１と同様に適正なゲル化状態にした。また、粘度は８４０ｃｐであった。結果を下記表２に示す。 <Example 2>
(Adjustment of ink composition)
The ink composition was prepared in the same manner as in Example 1 except that the addition amount of dimethyl sulfoxide was 15 parts by weight and the mixed alcohol was 200 parts by weight (isopropanol (160 parts by weight): propylene glycol (40 parts by weight)). Produced. This ink composition was brought into an appropriate gelation state as in Example 1. The viscosity was 840 cp. The results are shown in Table 2 below.
（透明導電膜の作製）
　実施例１と同様にしてスクリーン印刷により透明導電膜を作製した。スクリーン印刷の状態は、実施例１と同様に良好であった。得られた透明導電膜は、膜厚が９８０ｎｍであり、面積抵抗が２６１Ω／□であり、導電率が３９Ｓ／ｃｍであり、全光線透過率が８４．１％、ヘイズが１．０であった。結果を下記表３に示す。 (Preparation of transparent conductive film)
A transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1. The obtained transparent conductive film had a film thickness of 980 nm, an area resistance of 261 Ω / □, an electrical conductivity of 39 S / cm, a total light transmittance of 84.1%, and a haze of 1.0. It was. The results are shown in Table 3 below.
＜実施例３＞
（インク組成物の調整）
　ジメチルスルホキシドの添加量を１７．５重量部とし、混合アルコールを２５０重量部（イソプロパノール（２００重量部）：プロピレングリコール（５０重量部））としたこと以外は、実施例１と同様にしてインク組成物を作製した。このインク組成物は、実施例１と同様にゲル化した。また、粘度は５８０ｃｐであった。結果を下記表２に示す。 <Example 3>
(Adjustment of ink composition)
Ink composition was the same as in Example 1 except that the addition amount of dimethyl sulfoxide was 17.5 parts by weight and the mixed alcohol was 250 parts by weight (isopropanol (200 parts by weight): propylene glycol (50 parts by weight)). A product was made. This ink composition was gelled as in Example 1. The viscosity was 580 cp. The results are shown in Table 2 below.
（透明導電膜の作製）
　実施例１と同様にしてスクリーン印刷により透明導電膜を作製した。スクリーン印刷の状態は、実施例１と同様に良好であった。得られた透明導電膜は、膜厚が８９０ｎｍであり、面積抵抗が２６１Ω／□であり、導電率が２６Ｓ／ｃｍであり、全光線透過率が８０．２％、ヘイズが１．２であった。結果を下記表３に示す。 (Preparation of transparent conductive film)
A transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1. The obtained transparent conductive film had a film thickness of 890 nm, an area resistance of 261 Ω / □, an electrical conductivity of 26 S / cm, a total light transmittance of 80.2%, and a haze of 1.2. It was. The results are shown in Table 3 below.
＜比較例１＞
（インク組成物の調整）
　ジメチルスルホキシドの添加量を８．５重量部とし、混合アルコールを７０重量部（イソプロパノール（５６重量部）：プロピレングリコール（１６重量部））としたこと以外は、実施例１と同様にしてインク組成物を作製した。このインク組成物は、実施例１とは異なりゲル化しなかった。また、粘度は２６０ｃｐであった。結果を下記表２に示す。 <Comparative Example 1>
(Adjustment of ink composition)
Ink composition was the same as in Example 1 except that the amount of dimethyl sulfoxide added was 8.5 parts by weight, and the mixed alcohol was 70 parts by weight (isopropanol (56 parts by weight): propylene glycol (16 parts by weight)). A product was made. Unlike the example 1, this ink composition did not gel. The viscosity was 260 cp. The results are shown in Table 2 below.
（透明導電膜の作製）
　実施例１と同様にしてスクリーン印刷により透明導電膜を作製した。比較例１のインク組成物は、粘度が低いことからスクリーン印刷時にインク組成物の流れが大きく、透明導電膜の形状制御が不可能であった。得られた透明導電膜は、膜厚が３００ｎｍであり、面積抵抗は１１００Ω／□であり、導電率が３０Ｓ／ｃｍであり、全光線透過率が８６．５％、ヘイズが０．９であった。結果を下記表３に示す。 (Preparation of transparent conductive film)
A transparent conductive film was produced by screen printing in the same manner as in Example 1. Since the ink composition of Comparative Example 1 had a low viscosity, the flow of the ink composition was large during screen printing, and it was impossible to control the shape of the transparent conductive film. The obtained transparent conductive film had a thickness of 300 nm, an area resistance of 1100 Ω / □, an electrical conductivity of 30 S / cm, a total light transmittance of 86.5%, and a haze of 0.9. It was. The results are shown in Table 3 below.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表２及び表３から分かるように、シランカップリング剤を含有し、所定量の混合アルコールを含む場合には、インク組成物の適正なゲル化状態の濃度範囲が低濃度にシフトして適正なゲル化状態になることが分かる（実施例１から実施例３）。そして、適正なゲル化状態のインク組成物を用いることによりスクリーン印刷が可能となり、良好な膜厚、面積抵抗、導電率、全光線透過率及びヘイズを有する透明導電膜が得られることが分かる。これに対して、混合アルコールの含有量が少なすぎる場合や多すぎる場合には、インク組成物が適正なゲル化状態にならず、スクリーン印刷が不良となることが分かる（比較例１）。また、混合アルコールの含有量が少なすぎる場合には、インク組成物の流れが大きく、透明導電膜の形状制御ができない状態となった（比較例１）。また、混合アルコールの含有量が多すぎる場合には、透明導電膜の表面に凹凸が生じて梨地状態となり、部分的に連続な膜とはならなかった。このため、導電率が大幅に低下した。 As can be seen from Tables 2 and 3, when a silane coupling agent is included and a predetermined amount of mixed alcohol is included, the concentration range of the appropriate gelation state of the ink composition is shifted to a low concentration and the proper concentration range is obtained. It turns out that it will be in a gelled state (Example 1 to Example 3). And it turns out that screen printing becomes possible by using the ink composition of a suitable gelatinization state, and the transparent conductive film which has favorable film thickness, area resistance, electrical conductivity, total light transmittance, and haze is obtained. On the other hand, when the content of the mixed alcohol is too small or too large, it can be seen that the ink composition is not in an appropriate gelled state and the screen printing becomes poor (Comparative Example 1). In addition, when the content of the mixed alcohol was too small, the flow of the ink composition was large, and the shape of the transparent conductive film could not be controlled (Comparative Example 1). Moreover, when there was too much content of mixed alcohol, the unevenness | corrugation produced in the surface of the transparent conductive film, and it became a satin state, and it did not become a partially continuous film | membrane. For this reason, the electrical conductivity decreased significantly.
　次に、本発明者らは、ＰＥＤＯＴ／ＰＳＳ水溶液の濃度、シランカップリング剤の含有量、及び混合アルコールの含有量を変化させてインク組成物を作製し、作製したインク組成物を用いて得られた透明導電膜の物性について調べた（実施例４～実施例１１、比較例３から比較例５）。また、市販のインク組成物を用いて透明導電膜を作製し、作製した透明導電膜の物性を調べた。 Next, the inventors prepared an ink composition by changing the concentration of the aqueous PEDOT / PSS solution, the content of the silane coupling agent, and the content of the mixed alcohol, and obtained the ink composition using the ink composition thus prepared. The physical properties of the obtained transparent conductive film were examined (Examples 4 to 11, Comparative Examples 3 to 5). Moreover, the transparent conductive film was produced using the commercially available ink composition, and the physical property of the produced transparent conductive film was investigated.
＜実施例４＞
（インク組成物の調整）
　ＰＥＤＯＴ／ＰＳＳ水溶液の濃度を１．７重量％とし、シランカップリング剤を０．４３重量部とし、ジメチルスルホキシドの添加量を２０重量部とし、混合アルコールを３００重量部（イソプロパノール（１００重量部）：プロピレングリコール（２００重量部））としたこと以外は、実施例１と同様にしてインク組成物を作製した。このインク組成物は、実施例１と同様に適切なゲル化状態となった。また、粘度は４００ｃｐであった。結果を下記表４に示す。 <Example 4>
(Adjustment of ink composition)
The concentration of the aqueous PEDOT / PSS solution is 1.7% by weight, the silane coupling agent is 0.43 parts by weight, the amount of dimethyl sulfoxide added is 20 parts by weight, and the mixed alcohol is 300 parts by weight (isopropanol (100 parts by weight)). : Propylene glycol (200 parts by weight)), an ink composition was prepared in the same manner as in Example 1. This ink composition was in an appropriate gelled state as in Example 1. The viscosity was 400 cp. The results are shown in Table 4 below.
（透明導電膜の作製）
　実施例１と同様にしてスクリーン印刷により透明導電膜を作製した。スクリーン印刷の状態は、実施例１と同様に良好であった。得られた透明導電膜は、膜厚が４５ｎｍであり、面積抵抗が７５０Ω／□であり、導電率が２９０Ｓ／ｃｍであり、全光線透過率が８７％であり、ヘイズが０．９であった。結果を下記表５に示す。 (Preparation of transparent conductive film)
A transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1. The obtained transparent conductive film had a film thickness of 45 nm, a sheet resistance of 750 Ω / □, a conductivity of 290 S / cm, a total light transmittance of 87%, and a haze of 0.9. It was. The results are shown in Table 5 below.
＜実施例５＞
（インク組成物の調整）
　ＰＥＤＯＴ／ＰＳＳ水溶液の濃度を２．２重量％とし、シランカップリング剤を０．５５重量部としたこと以外は、実施例４と同様にしてインク組成物を作製した。このインク組成物は、実施例４と同様に適正なゲル化状態となった。また、粘度は５３０ｃｐであった。結果を下記表４に示す。 <Example 5>
(Adjustment of ink composition)
An ink composition was prepared in the same manner as in Example 4 except that the concentration of the PEDOT / PSS aqueous solution was 2.2 wt% and the silane coupling agent was 0.55 parts by weight. This ink composition was in an appropriate gelled state as in Example 4. The viscosity was 530 cp. The results are shown in Table 4 below.
（透明導電膜の作製）
　実施例１と同様にしてスクリーン印刷により透明導電膜を作製した。スクリーン印刷の状態は、実施例１と同様に良好であった。得られた透明導電膜は、膜厚が６０ｎｍであり、面積抵抗が３４３Ω／□であり、導電率が４９０Ｓ／ｃｍであり、全光線透過率が８８％であり、ヘイズが０．８であった。結果を下記表５に示す。 (Preparation of transparent conductive film)
A transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1. The obtained transparent conductive film had a film thickness of 60 nm, a sheet resistance of 343 Ω / □, a conductivity of 490 S / cm, a total light transmittance of 88%, and a haze of 0.8. It was. The results are shown in Table 5 below.
＜実施例６＞
（インク組成物の調整）
　ＰＥＤＯＴ／ＰＳＳ水溶液の濃度を２．５重量％とし、シランカップリング剤を０．６３重量部とし、混合アルコールを３００重量部（イソプロパノール（６０重量部）：プロピレングリコール（２４０重量部））としたこと以外は、実施例４と同様にしてインク組成物を作製した。このインク組成物は、実施例４と同様に適正なゲル化状態となった。また、粘度は６００ｃｐであった。結果を下記表４に示す。 <Example 6>
(Adjustment of ink composition)
The concentration of the aqueous solution of PEDOT / PSS was 2.5% by weight, the silane coupling agent was 0.63 parts by weight, and the mixed alcohol was 300 parts by weight (isopropanol (60 parts by weight): propylene glycol (240 parts by weight)). Except for this, an ink composition was prepared in the same manner as in Example 4. This ink composition was in an appropriate gelled state as in Example 4. The viscosity was 600 cp. The results are shown in Table 4 below.
（透明導電膜の作製）
　実施例１と同様にしてスクリーン印刷により透明導電膜を作製した。スクリーン印刷の状態は、実施例１と同様に良好であった。得られた透明導電膜は、膜厚が７５ｎｍであり、面積抵抗が２９０Ω／□であり、導電率が４６０Ｓ／ｃｍであり、全光線透過率が８８％であり、ヘイズが０．８であった。結果を下記表５に示す。 (Preparation of transparent conductive film)
A transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1. The obtained transparent conductive film had a film thickness of 75 nm, a sheet resistance of 290 Ω / □, a conductivity of 460 S / cm, a total light transmittance of 88%, and a haze of 0.8. It was. The results are shown in Table 5 below.
＜実施例７＞
（インク組成物の調整）
　ＰＥＤＯＴ／ＰＳＳ水溶液の濃度を２．５重量％とし、シランカップリング剤を０．６３重量部とし、混合アルコールを３００重量部（イソプロパノール（５０重量部）：プロピレングリコール（２５０重量部））としたこと以外は、実施例４と同様にしてインク組成物を作製した。このインク組成物は、実施例１と同様に適正なゲル化状態となった。また、粘度は６００ｃｐであった。結果を下記表４に示す。 <Example 7>
(Adjustment of ink composition)
The concentration of the PEDOT / PSS aqueous solution was 2.5% by weight, the silane coupling agent was 0.63 parts by weight, and the mixed alcohol was 300 parts by weight (isopropanol (50 parts by weight): propylene glycol (250 parts by weight)). Except for this, an ink composition was prepared in the same manner as in Example 4. This ink composition was in an appropriate gelled state as in Example 1. The viscosity was 600 cp. The results are shown in Table 4 below.
（透明導電膜の作製）
　実施例１と同様にしてスクリーン印刷により透明導電膜を作製した。スクリーン印刷の状態は、実施例１と同様に良好であった。得られた透明導電膜は、膜厚が７２ｎｍであり、面積抵抗が２６０Ω／□であり、導電率が５３３Ｓ／ｃｍであり、全光線透過率が８８％であり、ヘイズが０．８であった。結果を下記表５に示す。 (Preparation of transparent conductive film)
A transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1. The obtained transparent conductive film had a film thickness of 72 nm, a sheet resistance of 260 Ω / □, a conductivity of 533 S / cm, a total light transmittance of 88%, and a haze of 0.8. It was. The results are shown in Table 5 below.
＜実施例８＞
（インク組成物の調整）
　ＰＥＤＯＴ／ＰＳＳ水溶液の濃度を２．６重量％とし、シランカップリング剤を０．６５重量部とし、混合アルコールを３００重量部（イソプロパノール（１３０重量部）：プロピレングリコール（１７０重量部））としたこと以外は、実施例４と同様にしてインク組成物を作製した。このインク組成物は、実施例１と同様に適正なゲル化状態となった。また、粘度は６６０ｃｐであった。結果を下記表４に示す。 <Example 8>
(Adjustment of ink composition)
The concentration of the aqueous solution of PEDOT / PSS was 2.6% by weight, the silane coupling agent was 0.65 parts by weight, and the mixed alcohol was 300 parts by weight (isopropanol (130 parts by weight): propylene glycol (170 parts by weight)). Except for this, an ink composition was prepared in the same manner as in Example 4. This ink composition was in an appropriate gelled state as in Example 1. The viscosity was 660 cp. The results are shown in Table 4 below.
（透明導電膜の作製）
　実施例１と同様にしてスクリーン印刷により透明導電膜を作製した。スクリーン印刷の状態は、実施例１と同様に良好であった。得られた透明導電膜は、膜厚が８０ｎｍであり、面積抵抗が２５０Ω／□であり、導電率が５００Ｓ／ｃｍであり、全光線透過率が８７％であり、ヘイズが０．９であった。結果を下記表５に示す。 (Preparation of transparent conductive film)
A transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1. The obtained transparent conductive film had a film thickness of 80 nm, a sheet resistance of 250 Ω / □, a conductivity of 500 S / cm, a total light transmittance of 87%, and a haze of 0.9. It was. The results are shown in Table 5 below.
＜実施例９＞
（インク組成物の調整）
　ＰＥＤＯＴ／ＰＳＳ水溶液の濃度を２．８重量％とし、シランカップリング剤を０．７０重量部とし、混合アルコールを３００重量部（イソプロパノール（４０重量部）：プロピレングリコール（２６０重量部））としたこと以外は、実施例４と同様にしてインク組成物を作製した。このインク組成物は、実施例１と同様に適正なゲル化状態となった。また、粘度は７９０ｃｐであった。結果を下記表４に示す。 <Example 9>
(Adjustment of ink composition)
The concentration of the aqueous PEDOT / PSS solution was 2.8% by weight, the silane coupling agent was 0.70 part by weight, and the mixed alcohol was 300 parts by weight (isopropanol (40 parts by weight): propylene glycol (260 parts by weight)). Except for this, an ink composition was prepared in the same manner as in Example 4. This ink composition was in an appropriate gelled state as in Example 1. The viscosity was 790 cp. The results are shown in Table 4 below.
（透明導電膜の作製）
　実施例１と同様にしてスクリーン印刷により透明導電膜を作製した。スクリーン印刷の状態は、実施例１と同様に良好であった。得られた透明導電膜は、膜厚が１０５ｎｍであり、面積抵抗が２１０Ω／□であり、導電率が４５３Ｓ／ｃｍであり、全光線透過率が８６％であり、ヘイズが０．９であった。結果を下記表５に示す。 (Preparation of transparent conductive film)
A transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1. The obtained transparent conductive film had a film thickness of 105 nm, a sheet resistance of 210 Ω / □, a conductivity of 453 S / cm, a total light transmittance of 86%, and a haze of 0.9. It was. The results are shown in Table 5 below.
＜実施例１０＞
（インク組成物の調整）
　ＰＥＤＯＴ／ＰＳＳ水溶液の濃度を２．９重量％とし、シランカップリング剤を０．７３重量部とし、混合アルコールを３００重量部（イソプロパノール（１４０重量部）：プロピレングリコール（１６０重量部））としたこと以外は、実施例４と同様にしてインク組成物を作製した。このインク組成物は、実施例１と同様に適正なゲル化状態となった。また、粘度は８３０ｃｐであった。結果を下記表４に示す。 <Example 10>
(Adjustment of ink composition)
The concentration of the PEDOT / PSS aqueous solution was 2.9% by weight, the silane coupling agent was 0.73 parts by weight, and the mixed alcohol was 300 parts by weight (isopropanol (140 parts by weight): propylene glycol (160 parts by weight)). Except for this, an ink composition was prepared in the same manner as in Example 4. This ink composition was in an appropriate gelled state as in Example 1. The viscosity was 830 cp. The results are shown in Table 4 below.
（透明導電膜の作製）
　実施例１と同様にしてスクリーン印刷により透明導電膜を作製した。スクリーン印刷の状態は、実施例１と同様に良好であった。得られた透明導電膜は、膜厚が１２０ｎｍであり、面積抵抗が２０５Ω／□であり、導電率が４０７Ｓ／ｃｍであり、全光線透過率が８５％であり、ヘイズが１．０であった。結果を下記表５に示す。 (Preparation of transparent conductive film)
A transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1. The obtained transparent conductive film had a thickness of 120 nm, an area resistance of 205Ω / □, an electrical conductivity of 407 S / cm, a total light transmittance of 85%, and a haze of 1.0. It was. The results are shown in Table 5 below.
＜実施例１１＞
（インク組成物の調整）
　ＰＥＤＯＴ／ＰＳＳ水溶液の濃度を３．３重量％とし、シランカップリング剤を０．８３重量部とし、混合アルコールを３００重量部（イソプロパノール（１００重量部）：プロピレングリコール（２００重量部））としたこと以外は、実施例４と同様にしてインク組成物を作製した。このインク組成物は、実施例１と同様に適正なゲル化状態となった。また、粘度は９２０ｃｐであった。結果を下記表４に示す。 <Example 11>
(Adjustment of ink composition)
The concentration of the aqueous solution of PEDOT / PSS was 3.3% by weight, the silane coupling agent was 0.83 parts by weight, and the mixed alcohol was 300 parts by weight (isopropanol (100 parts by weight): propylene glycol (200 parts by weight)). Except for this, an ink composition was prepared in the same manner as in Example 4. This ink composition was in an appropriate gelled state as in Example 1. The viscosity was 920 cp. The results are shown in Table 4 below.
（透明導電膜の作製）
　実施例１と同様にしてスクリーン印刷により透明導電膜を作製した。スクリーン印刷の状態は、実施例１と同様に良好であった。得られた透明導電膜は、膜厚が１３５ｎｍであり、面積抵抗が３５０Ω／□であり、導電率が２１１Ｓ／ｃｍであり、全光線透過率が８４％であり、ヘイズが１．２であった。結果を下記表５に示す。 (Preparation of transparent conductive film)
A transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1. The obtained transparent conductive film had a film thickness of 135 nm, a sheet resistance of 350 Ω / □, a conductivity of 211 S / cm, a total light transmittance of 84%, and a haze of 1.2. It was. The results are shown in Table 5 below.
＜実施例１２＞
（インク組成物の調整）
　混合アルコールを３００重量部（プロピレングリコールモノメチルエーテル（５０重量部）：プロピレングリコール（２５０重量部））としたこと以外は、実施例７と同様にしてインク組成物を作製した。このインク組成物は、実施例１と同様に適正なゲル化状態となった。また、粘度は５６０ｃｐであった。結果を下記表４に示す。 <Example 12>
(Adjustment of ink composition)
An ink composition was prepared in the same manner as in Example 7, except that the mixed alcohol was 300 parts by weight (propylene glycol monomethyl ether (50 parts by weight): propylene glycol (250 parts by weight)). This ink composition was in an appropriate gelled state as in Example 1. The viscosity was 560 cp. The results are shown in Table 4 below.
（透明導電膜の作製）
　実施例１と同様にしてスクリーン印刷により透明導電膜を作製した。スクリーン印刷の状態は、実施例１と同様に良好であった。得られた透明導電膜は、膜厚が６４ｎｍであり、面積抵抗が３００Ω／□であり、導電率が５２０Ｓ／ｃｍであり、全光線透過率が８８％であり、ヘイズが０．８であった。結果を下記表５に示す。 (Preparation of transparent conductive film)
A transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1. The obtained transparent conductive film had a film thickness of 64 nm, a sheet resistance of 300 Ω / □, a conductivity of 520 S / cm, a total light transmittance of 88%, and a haze of 0.8. It was. The results are shown in Table 5 below.
＜比較例２＞
（インク組成物の調整）
　ＰＥＤＯＴ／ＰＳＳ水溶液の濃度を３．５重量％とし、実施例４と同様にしてインク組成物の調製を試みたが、インク組成物が析出・固化し、その後の操作ができなかった。結果を下記表６及び下記表７に示す。 <Comparative Example 2>
(Adjustment of ink composition)
The concentration of the PEDOT / PSS aqueous solution was set to 3.5% by weight, and an ink composition was prepared in the same manner as in Example 4. However, the ink composition precipitated and solidified, and the subsequent operation was not possible. The results are shown in Table 6 and Table 7 below.
＜比較例３＞
（インク組成物の調整）
　ＰＥＤＯＴ／ＰＳＳ水溶液の濃度を１．１重量％とし、シランカップリング剤を０．３重量部とし、混合アルコールを３００重量部（イソプロパノール（５０重量部）：プロピレングリコール（３５０重量部））としたこと以外は、実施例４と同様にしてインク組成物を作製した。このインク組成物は、比較例１と同様に適正なゲル化状態にならなかった。また、粘度は２３０ｃｐであった。結果を下記表６に示す。 <Comparative Example 3>
(Adjustment of ink composition)
The concentration of the PEDOT / PSS aqueous solution was 1.1% by weight, the silane coupling agent was 0.3 parts by weight, and the mixed alcohol was 300 parts by weight (isopropanol (50 parts by weight): propylene glycol (350 parts by weight)). Except for this, an ink composition was prepared in the same manner as in Example 4. This ink composition did not become an appropriate gelled state as in Comparative Example 1. The viscosity was 230 cp. The results are shown in Table 6 below.
（透明導電膜の作製）
　実施例１と同様にしてスクリーン印刷により透明導電膜を作製した。スクリーン印刷の状態は、実施例１と同様に良好であった。得られた透明導電膜は、膜厚が２７ｎｍであり、面積抵抗が１２００Ω／□であり、導電率が３０９Ｓ／ｃｍであり、全光線透過率が８８％であり、ヘイズが０．９であった。結果を下記表７に示す。 (Preparation of transparent conductive film)
A transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1. The obtained transparent conductive film had a film thickness of 27 nm, a sheet resistance of 1200 Ω / □, a conductivity of 309 S / cm, a total light transmittance of 88%, and a haze of 0.9. It was. The results are shown in Table 7 below.
＜比較例４＞
（インク組成物の調整）
　ＰＥＤＯＴ／ＰＳＳ水溶液の濃度を１．２重量％とし、シランカップリング剤を０．３重量部とし、混合アルコールを３００重量部（イソプロパノール（１００重量部）：プロピレングリコール（２００重量部））としたこと以外は、実施例４と同様にしてインク組成物を作製した。このインク組成物は、比較例１と同様に適正なゲル化状態にならなかった。また、粘度は２６０ｃｐであった。結果を下記表６に示す。 <Comparative example 4>
(Adjustment of ink composition)
The concentration of the PEDOT / PSS aqueous solution was 1.2% by weight, the silane coupling agent was 0.3 parts by weight, and the mixed alcohol was 300 parts by weight (isopropanol (100 parts by weight): propylene glycol (200 parts by weight)). Except for this, an ink composition was prepared in the same manner as in Example 4. This ink composition did not become an appropriate gelled state as in Comparative Example 1. The viscosity was 260 cp. The results are shown in Table 6 below.
（透明導電膜の作製）
　実施例１と同様にしてスクリーン印刷により透明導電膜を作製した。スクリーン印刷の状態は、実施例１と同様に良好であった。得られた透明導電膜は、膜厚が３０ｎｍであり、面積抵抗が１２００Ω／□であり、導電率が２７８Ｓ／ｃｍであり、全光線透過率が８８％であり、ヘイズが０．９であった。結果を下記表７に示す。 (Preparation of transparent conductive film)
A transparent conductive film was produced by screen printing in the same manner as in Example 1. The screen printing state was as good as in Example 1. The obtained transparent conductive film had a film thickness of 30 nm, a sheet resistance of 1200 Ω / □, a conductivity of 278 S / cm, a total light transmittance of 88%, and a haze of 0.9. It was. The results are shown in Table 7 below.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　表４から表７から分かるように、ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が所定範囲内にある場合には、シランカップリング剤の含有量や混合アルコールの組成を変化させた場合においても、広い範囲でゲル化が可能となることが分かる(実施例４から実施例１２)。これに対して、表５及び表６から分かるように、ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が高すぎる場合には、析出・固化しインク組成物として取り扱うことが不可能となり（比較例２）、ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が低すぎる場合には、インク組成物の適正なゲル化状態が得られなくなることが分かる（比較例３及び比較例４）。 As can be seen from Table 4 to Table 7, when the concentration of the aqueous solution of PEDOT / PSS is within a predetermined range, even when the content of the silane coupling agent and the composition of the mixed alcohol are changed, the gel is in a wide range. It can be seen that this can be achieved (Examples 4 to 12). On the other hand, as can be seen from Tables 5 and 6, when the concentration of the PEDOT / PSS aqueous solution is too high, it becomes precipitated and solidified and cannot be handled as an ink composition (Comparative Example 2). It can be seen that when the concentration of the PSS aqueous solution is too low, an appropriate gelled state of the ink composition cannot be obtained (Comparative Example 3 and Comparative Example 4).
　なお、本発明は上記実施の形態に限定されず、種々変更して実施することが可能である。上記実施の形態において、添付図面に図示されている大きさや形状などについては、これに限定されず、本発明の効果を発揮する範囲内で適宜変更することが可能である。その他、本発明の目的の範囲を逸脱しない限りにおいて適宜変更して実施することが可能である。 It should be noted that the present invention is not limited to the above embodiment, and can be implemented with various modifications. In the above-described embodiment, the size, shape, and the like illustrated in the accompanying drawings are not limited to this, and can be appropriately changed within a range in which the effect of the present invention is exhibited. In addition, various modifications can be made without departing from the scope of the object of the present invention.
　本発明は、スクリーン印刷方式による透明導電膜の形成が可能であり、しかも導電率及び透過率に優れた透明導電膜が得られるインク組成物及びインク組成物の製造方法を実現できるという効果を有し、特に、液晶ディスプレイ、エレクトロルミネッセンスディスプレイ、プラズマディスプレイ、エレクトロクロミックディスプレイ、太陽電池、タッチパネル、電子ペーパー等に用いられる透明電極及び電磁波シールドなど、各種透明導電膜を用いたデバイスに適用可能である。 INDUSTRIAL APPLICABILITY The present invention has an effect that a transparent conductive film can be formed by a screen printing method, and an ink composition capable of obtaining a transparent conductive film having excellent conductivity and transmittance and a method for producing the ink composition can be realized. In particular, the present invention is applicable to devices using various transparent conductive films such as a liquid crystal display, an electroluminescence display, a plasma display, an electrochromic display, a transparent electrode and an electromagnetic wave shield used for solar cells, touch panels, and electronic paper.
　１１　ＰＥＤＯＴ
　１２　ＰＳＳ
　１３　シランカップリング剤
　２１　ＰＥＤＯＴ分子
　２２　ＰＳＳ分子 11 PEDOT
12 PSS
13 Silane coupling agent 21 PEDOT molecule 22 PSS molecule

Claims (17)

  1. 　ＰＥＤＯＴ／ＰＳＳ水溶液１００重量部と、混合アルコール３００重量部以下と、シランカップリング剤と、を混合した溶液をインク化してなり、前記ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が下記関係式（１）を満たし、前記混合アルコールが低粘性溶媒と高粘性アルコールとを含むことを特徴とするインク組成物。
    式（１）
    　１．３重量％≦ＰＥＤＯＴ／ＰＳＳ水溶液＜３．５重量％     A solution obtained by mixing 100 parts by weight of a PEDOT / PSS aqueous solution, 300 parts by weight or less of a mixed alcohol, and a silane coupling agent is converted into an ink, and the concentration of the PEDOT / PSS aqueous solution satisfies the following relational expression (1). An ink composition, wherein the mixed alcohol contains a low-viscosity solvent and a high-viscosity alcohol.
    Formula (1)
    1.3 wt% ≦ PEDOT / PSS aqueous solution <3.5 wt%
  2. 　前記低粘性溶媒が低級アルコールであることを特徴とする請求項１記載のインク組成物。 The ink composition according to claim 1, wherein the low-viscosity solvent is a lower alcohol.
  3. 　前記低級アルコールがメタノール、エタノール又はプロパノールであることを特徴とする請求項２記載のインク組成物。 3. The ink composition according to claim 2, wherein the lower alcohol is methanol, ethanol or propanol.
  4. 　前記低粘性溶媒がグリコールモノアルキルエーテルであることを特徴とする請求項１記載のインク組成物。 2. The ink composition according to claim 1, wherein the low-viscosity solvent is glycol monoalkyl ether.
  5. 　前記高粘性アルコールがグリコールであることを特徴とする請求項１から請求項４のいずれかに記載のインク組成物。 The ink composition according to any one of claims 1 to 4, wherein the highly viscous alcohol is glycol.
  6. 　前記グリコールがプロピレングリコール又はブタンジオールであることを特徴とする請求項５記載のインク組成物。 6. The ink composition according to claim 5, wherein the glycol is propylene glycol or butanediol.
  7. 　前記ＰＥＤＯＴ／ＰＳＳ水溶液１００重量部と、前記混合アルコール３００重量部と、を含むことを特徴とする請求項１から請求項６のいずれかに記載のインク組成物。 The ink composition according to any one of claims 1 to 6, comprising 100 parts by weight of the PEDOT / PSS aqueous solution and 300 parts by weight of the mixed alcohol.
  8. 　前記低粘性溶媒と前記高粘性アルコールとの混合比（低粘性溶媒：高粘性アルコール）が４：１であることを特徴とする請求項１から請求項６のいずれかに記載のインク組成物。 The ink composition according to any one of claims 1 to 6, wherein a mixing ratio of the low viscosity solvent and the high viscosity alcohol (low viscosity solvent: high viscosity alcohol) is 4: 1.
  9. 　前記ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が下記関係式（２）を満たし、前記混合アルコールが前記低粘性溶媒１００重量部以上１５０重量部以下と前記高粘性アルコール２００重量部以下１５０重量部以上とを含むことを特徴とする請求項７記載のインク組成物。
    式（２）
    　１．３重量％≦ＰＥＤＯＴ／ＰＳＳ水溶液＜２．０重量％     The concentration of the aqueous solution of PEDOT / PSS satisfies the following relational expression (2), and the mixed alcohol includes 100 parts by weight or more and 150 parts by weight or less of the low-viscosity solvent and 200 parts by weight or less of the high-viscosity alcohol. The ink composition according to claim 7.
    Formula (2)
    1.3 wt% ≦ PEDOT / PSS aqueous solution <2.0 wt%
  10. 　前記ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が下記関係式（３）を満たし、前記混合アルコールが前記低粘性溶媒１５重量部以上１８０重量部以下と前記高粘性アルコール２８５重量部以下１２０重量部以上とを含むことを特徴とする請求項７記載のインク組成物。
    式（３）
    　２．０重量％≦ＰＥＤＯＴ／ＰＳＳ水溶液＜３．０重量％     The concentration of the aqueous solution of PEDOT / PSS satisfies the following relational expression (3), and the mixed alcohol includes 15 parts by weight or more and 180 parts by weight or less of the low viscosity solvent and 285 parts by weight or less of the high viscosity alcohol. The ink composition according to claim 7.
    Formula (3)
    2.0 wt% ≦ PEDOT / PSS aqueous solution <3.0 wt%
  11. 　前記ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が下記関係式（４）を満たし、前記混合アルコールが前記低粘性溶媒１０重量部以上２００重量部以下と前記高粘性アルコール２９０重量部以下１００重量部以上とを含むことを特徴とする請求項７記載のインク組成物。
    式（４）
    　３．０重量％≦ＰＥＤＯＴ／ＰＳＳ水溶液＜３．５重量％     The concentration of the aqueous solution of PEDOT / PSS satisfies the following relational expression (4), and the mixed alcohol includes 10 parts by weight or more and 200 parts by weight or less of the low viscosity solvent and 290 parts by weight or less of the high viscosity alcohol 100 parts by weight or more. The ink composition according to claim 7.
    Formula (4)
    3.0 wt% ≦ PEDOT / PSS aqueous solution <3.5 wt%
  12. 　前記ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が下記関係式（２）を満たし、前記混合アルコールが前記低粘性溶媒８０重量部以上２００重量部以下と前記高粘性アルコール２０重量部以下５０重量部以上とを含むことを特徴とする請求項８記載のインク組成物。
    式（２）
    　１．３重量％≦ＰＥＤＯＴ／ＰＳＳ水溶液＜２．０重量％     The concentration of the aqueous solution of PEDOT / PSS satisfies the following relational expression (2), and the mixed alcohol contains 80 to 200 parts by weight of the low-viscosity solvent and 20 to 50 parts by weight of the high-viscosity alcohol. The ink composition according to claim 8.
    Formula (2)
    1.3 wt% ≦ PEDOT / PSS aqueous solution <2.0 wt%
  13. 　前記ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が下記関係式（３）を満たし、前記混合アルコールが前記低粘性溶媒１０重量部以上２２０重量部以下と前記高粘性アルコール２重量部以上５５重量部以下とを含むことを特徴とする請求項８記載のインク組成物。
    式（３）
    　２．０重量％≦ＰＥＤＯＴ／ＰＳＳ水溶液＜３．０重量％     The concentration of the aqueous solution of PEDOT / PSS satisfies the following relational expression (3), and the mixed alcohol includes 10 to 220 parts by weight of the low viscosity solvent and 2 to 55 parts by weight of the high viscosity alcohol. The ink composition according to claim 8.
    Formula (3)
    2.0 wt% ≦ PEDOT / PSS aqueous solution <3.0 wt%
  14. 　前記ＰＥＤＯＴ／ＰＳＳ水溶液の濃度が下記関係式（４）を満たし、前記混合アルコールが前記低粘性溶媒５重量部以上２５０重量部以下と前記高粘性アルコール１重量部以上６５重量部以下とを含むことを特徴とする請求項８記載のインク組成物。
    式（４）
    　３．０重量％≦ＰＥＤＯＴ／ＰＳＳ水溶液＜３．５重量％     The concentration of the aqueous solution of PEDOT / PSS satisfies the following relational expression (4), and the mixed alcohol includes 5 to 250 parts by weight of the low-viscosity solvent and 1 to 65 parts by weight of the high-viscosity alcohol. The ink composition according to claim 8.
    Formula (4)
    3.0 wt% ≦ PEDOT / PSS aqueous solution <3.5 wt%
  15. 　請求項１から請求項１４のいずれかに記載のインク組成物の製造方法であって、前記ＰＥＤＯＴ／ＰＳＳ水溶液と、前記混合アルコールと、前記シランカップリング剤と、を含む溶液を撹拌してゲル化するゲル化工程と、ゲル化した前記溶液をインク化してインク組成物を製造するインク化工程と、を含むことを特徴とするインク組成物の製造方法。 The method for producing an ink composition according to any one of claims 1 to 14, wherein a solution containing the PEDOT / PSS aqueous solution, the mixed alcohol, and the silane coupling agent is stirred to obtain a gel. A method for producing an ink composition comprising: a gelling step for forming an ink; and an ink forming step for producing an ink composition by converting the gelled solution into an ink.
  16. 　請求項１から請求項１４のいずれかに記載のインク組成物を用いて形成されたことを特徴とする透明導電膜。 A transparent conductive film formed using the ink composition according to any one of claims 1 to 14.
  17. 　請求項１５に記載のインク組成物の製造方法によって製造されたインク組成物を用いることを特徴とする透明導電膜の製造方法。 A method for producing a transparent conductive film, wherein the ink composition produced by the method for producing an ink composition according to claim 15 is used.
PCT/JP2013/070637 2012-08-09 2013-07-30 Ink composition, ink-composition production method, transparent conductive film, and transparent-conductive-film production method WO2014024735A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012177489A JP2015180708A (en) 2012-08-09 2012-08-09 Ink composition, production method of ink composition, transparent conductive film, and production method of transparent conductive film
JP2012-177489 2012-08-09

Publications (1)

Publication Number Publication Date
WO2014024735A1 true WO2014024735A1 (en) 2014-02-13

Family

ID=50067966

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/070637 WO2014024735A1 (en) 2012-08-09 2013-07-30 Ink composition, ink-composition production method, transparent conductive film, and transparent-conductive-film production method

Country Status (2)

Country Link
JP (1) JP2015180708A (en)
WO (1) WO2014024735A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103928614A (en) * 2014-04-21 2014-07-16 电子科技大学 Organic thin film solar cell with high fill factors
CN106810945A (en) * 2015-11-30 2017-06-09 比亚迪股份有限公司 Conductive ink composition and its application process and conductive ink material layer and electronic equipment and printer
JP2018104633A (en) * 2016-12-28 2018-07-05 日本合成化学工業株式会社 Resin solution, and resin layer and adhesive sheet using the same
CN111410870A (en) * 2020-02-16 2020-07-14 陕西科技大学 Organic conductive polymer ink and anti-counterfeiting system based on screen printing and manufacturing method thereof
CN113053565A (en) * 2021-06-02 2021-06-29 苏州华星光电技术有限公司 Conductive film, preparation method thereof and display panel

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009040969A (en) * 2007-08-10 2009-02-26 Shin Etsu Polymer Co Ltd Water-repellent electrically conductive polymer coating material and water-repellent electrically conductive coating film
WO2009044894A1 (en) * 2007-10-05 2009-04-09 Shin-Etsu Polymer Co., Ltd. Conductive polymer solution, conductive coating film, and input device
JP2009170408A (en) * 2007-12-20 2009-07-30 Shin Etsu Polymer Co Ltd Conductive sheet, manufacturing method therefor, and input device
JP2010114066A (en) * 2008-10-06 2010-05-20 Fujifilm Corp Organic conductive polymer coating liquid, organic conductive polymer film, conductor, and resistive film type touch panel
JP2010146944A (en) * 2008-12-22 2010-07-01 Shin Etsu Polymer Co Ltd Conductive sheet, method of manufacturing the same, and input device
WO2011099474A1 (en) * 2010-02-09 2011-08-18 王子製紙株式会社 Conductive laminate and touch panel using same
WO2012057257A1 (en) * 2010-10-29 2012-05-03 信越ポリマー株式会社 Transparent conductive glass substrate

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009040969A (en) * 2007-08-10 2009-02-26 Shin Etsu Polymer Co Ltd Water-repellent electrically conductive polymer coating material and water-repellent electrically conductive coating film
WO2009044894A1 (en) * 2007-10-05 2009-04-09 Shin-Etsu Polymer Co., Ltd. Conductive polymer solution, conductive coating film, and input device
JP2009170408A (en) * 2007-12-20 2009-07-30 Shin Etsu Polymer Co Ltd Conductive sheet, manufacturing method therefor, and input device
JP2010114066A (en) * 2008-10-06 2010-05-20 Fujifilm Corp Organic conductive polymer coating liquid, organic conductive polymer film, conductor, and resistive film type touch panel
JP2010146944A (en) * 2008-12-22 2010-07-01 Shin Etsu Polymer Co Ltd Conductive sheet, method of manufacturing the same, and input device
WO2011099474A1 (en) * 2010-02-09 2011-08-18 王子製紙株式会社 Conductive laminate and touch panel using same
WO2012057257A1 (en) * 2010-10-29 2012-05-03 信越ポリマー株式会社 Transparent conductive glass substrate

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103928614A (en) * 2014-04-21 2014-07-16 电子科技大学 Organic thin film solar cell with high fill factors
CN103928614B (en) * 2014-04-21 2016-08-17 电子科技大学 A kind of organic thin film solar cell of high fill factor
CN106810945A (en) * 2015-11-30 2017-06-09 比亚迪股份有限公司 Conductive ink composition and its application process and conductive ink material layer and electronic equipment and printer
CN106810945B (en) * 2015-11-30 2019-09-13 比亚迪股份有限公司 Conductive ink composition and its application method and conductive ink material layer and electronic equipment and printer
JP2018104633A (en) * 2016-12-28 2018-07-05 日本合成化学工業株式会社 Resin solution, and resin layer and adhesive sheet using the same
CN111410870A (en) * 2020-02-16 2020-07-14 陕西科技大学 Organic conductive polymer ink and anti-counterfeiting system based on screen printing and manufacturing method thereof
CN113053565A (en) * 2021-06-02 2021-06-29 苏州华星光电技术有限公司 Conductive film, preparation method thereof and display panel

Also Published As

Publication number Publication date
JP2015180708A (en) 2015-10-15

Similar Documents

Publication Publication Date Title
WO2014024735A1 (en) Ink composition, ink-composition production method, transparent conductive film, and transparent-conductive-film production method
KR100442408B1 (en) Polythiophene Conductive Polymer Solution Composition with High Conductivity and High Transparency
JP2007531233A (en) Composition for coating organic electrode and method for producing highly transparent organic electrode using the same
JP5232867B2 (en) Polythiophene-based conductive polymer film
US7683124B2 (en) Dispersions of intrinsically conductive polymers, and methods for the production thereof
JP6005832B2 (en) Curable antistatic organopolysiloxane composition and antistatic silicone coating
JP2019039019A (en) Conductive composition, antistatic resin composition and antistatic resin coated film
Liu et al. Enhancements in conductivity and thermal and conductive stabilities of electropolymerized polypyrrole with caprolactam-modified clay
CN104449377A (en) Graphene conductive coating and preparation method thereof
KR20110073272A (en) Conductive polymer composition and conductive film prepared from the composition
JP2012124107A (en) Method of manufacturing transparent conductive film, transparent conductive film, method of manufacturing conductive fiber, conductive fiber, carbon nanotube/conductive polymer composite dispersion liquid, method of manufacturing carbon nanotube/conductive polymer composite dispersion liquid, and electronic apparatus
Hasanin et al. Electrical properties of conducting tertiary composite based on biopolymers and polyaniline
JP6093779B2 (en) Conductive composition for forming back electrode of liquid crystal display device and method for forming back electrode using the same
Kwon et al. Elastomeric conducting polymer nano-composites derived from ionic liquid polymer stabilized-poly (3, 4-ethylenedioxythiophene)
Li et al. High water-stable, hard and strong-adhesive antistatic films from waterborne PEDOT: PSS composites
CN105331054A (en) Composite conductive film
JP2019075265A (en) Conductive particle and method for producing the same, and conductive resin composition
JP2012056990A (en) Conductive benzothiadiazole copolymer composition
Zhao et al. Ionic liquid induced supramolecular self-assembly of poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) thin films with enhanced conductivity and tunable nanoporosity
KR100475550B1 (en) Conductive black-colored coating composition for shielding electromagnetic waves, method for forming coating film using the same and the coating film
KR20110122677A (en) Conductive coating composition
JP2017502337A (en) Conductive composition for forming back electrode of liquid crystal display device
KR20090087530A (en) Transparence conductive coating composition
KR100417173B1 (en) Anti-Static Transparent Hard Coating Liquid Composition
KR20140145300A (en) Composition for high durable transparent conductive coating, manufacturing method of the composition and transparent conductive film using the composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13827976

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13827976

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP